WO2000061644A1 - Method for continuously producing polymers - Google Patents

Method for continuously producing polymers Download PDF

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Publication number
WO2000061644A1
WO2000061644A1 PCT/EP2000/002709 EP0002709W WO0061644A1 WO 2000061644 A1 WO2000061644 A1 WO 2000061644A1 EP 0002709 W EP0002709 W EP 0002709W WO 0061644 A1 WO0061644 A1 WO 0061644A1
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Prior art keywords
heat exchanger
weight
polymerization
spiral coil
coil heat
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PCT/EP2000/002709
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German (de)
French (fr)
Inventor
Paulus Schmaus
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Basf Aktiengesellschaft
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Publication of WO2000061644A1 publication Critical patent/WO2000061644A1/en

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    • 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
    • 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
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/243—Tubular reactors spirally, concentrically or zigzag wound
    • 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

Definitions

  • the present invention relates to an improved process for the continuous production of polymers from vinylaromatic compounds by bulk or solution polymerization.
  • reactors which are equipped with static mixing and cooling devices to fill the cross section. These are described, for example, in EP-B 0755945. These so-called static reactors are operated as loop reactors, i.e. part of the polymer solution is mixed with the feed, while another part is removed from the reactor and polymerized further in a downstream tubular reactor as a plug flow. This process is complex in terms of equipment.
  • the object of the invention was to find a process for the continuous production of polymers from vinylaromatic compounds by bulk or solution polymerization, which opens up the use of a relatively inexpensive reactor and which enables the polymerization to be carried out simply and effectively.
  • the polymerization carried out in the process according to the invention is highly exothermic.
  • the tubes of the spiral coil heat exchanger are advantageously flowed through with a heat transfer medium such as Diphyl®, Dowtherm S® or similar heat-resistant liquids for dissipating the heat of reaction.
  • the spiral arrangement of the tubes provides a large heat exchange surface, the tube volume in the total volume of the reactor generally not exceeding 10%.
  • the process according to the invention thus opens up an effective and economical heat dissipation and offers the possibility of carrying out the polymerization process in a manner which is easy to control in terms of process engineering.
  • the tubes within the spiral coil heat exchanger are arranged such that they are arranged at a distance of approximately 5 to 15 cm, preferably 8 to 10 cm, particularly preferably approximately 9 cm above the reactor cross section.
  • this can be provided with a double jacket or with half-shells.
  • the double jacket or the half-shells are flowed through by the same heat transfer medium as the pipes.
  • the spiral coil heat exchanger is preferably divided into 2 to 6 segments, which are flowed through independently of one another by heatable and coolable heat transfer medium.
  • the feed materials and any additives are preferably fed to the spiral coil heat exchanger from below.
  • the hydraulically filled, ie completely filled, reactor is preferably flowed through from bottom to top in a plug flow.
  • the Polymer solution can be fed to the degassing equipment directly without interposing a discharge pump.
  • the process according to the invention is preferably suitable for the continuous production of polymers from vinylaromatic
  • Styrene is used as the starting material in the presence of a solvent mixture containing styrene / ethylbenzene.
  • Additives such as mineral oil, zinc stearate and colorants can also be added.
  • the polymerisation reactions are described in detail, for example, in the plastics manual 4 "Polystyrene” Carl Hansen Verlag Chapter 3 "Production of Polystyrene”.
  • the reaction is carried out at temperatures of about 120 to 180 ° C., preferably at 130 to 170 ° C. and at pressures of 1 bar to 20 bar, preferably 5 to 10 bar.
  • the conversion of the process according to the invention is preferably carried out up to about 85% by weight. It can also be advisable to carry out the conversion up to about 90% by weight.
  • the tests were carried out in two reactors connected in series, each with 2 separate heating and cooling circuits.
  • the cooling circuits were heated or cooled with liquid heat transfer oil.
  • the total volume of a reactor is 10 liters.
  • a solution of styrene and ethylbenzene consisting of 62% by weight of styrene and 38% by weight of ethylbenzene, or 86% by weight of styrene and 14% by weight of ethylbenzene in an amount of 1 to 2 kg / h fed.
  • the polymer content at the outlet of the reactor was between 48% by weight and 80% by weight.
  • the polymer solution was then fed to a flash evaporator to remove the volatiles.
  • the viscosity number of the polymer was determined in accordance with DIN 53726.
  • the styrene concentration was 62% by weight, the polymerization temperature was 140 ° C. and the residence time was 20 hours.
  • a polymer content of 53% by weight was achieved.
  • the viscosity number was 58 ml / g.
  • the styrene concentration was 62% by weight, the polymerization temperature was 140 ° C. and the residence time was 10 hours.
  • a polymer content of 45% by weight was achieved.
  • the viscosity number was 61 ml / g.
  • the styrene concentration was 86.5% by weight, the polymerization temperature was 140 ° C. and the residence time was 10 hours.
  • a polymer content of 73% by weight was achieved.
  • the viscosity number was 62 ml / g.
  • the styrene concentration was 86.5% by weight, the polymerization temperature 130 ° C. in the first half and 140 ° C. in the second half of the polymerization, and the residence time was 20 hours.
  • a polymer content of 80% by weight was achieved.
  • the viscosity number was 77 ml / g.

Abstract

The invention relates to a method for continuously producing polymers comprised of vinyl aromatic compounds by means of mass polymerization or solvent polymerization, whereby the feed materials are fed into a spiral heat exchanger and are reacted therein.

Description

Verfahren zur kontinuierlichen Herstellung von Polymeren Process for the continuous production of polymers
Beschreibungdescription
Die vorliegende Erfindung betrifft ein verbessertes Verfahren zur kontinuierlichen Herstellung von Polymeren aus vinylaromatischen Verbindungen durch Masse- bzw. Lösungspolymerisation.The present invention relates to an improved process for the continuous production of polymers from vinylaromatic compounds by bulk or solution polymerization.
Die radikalische Polymerisation von vinylaromatischenThe radical polymerization of vinyl aromatic
Verbindungen wie Styrol, gegebenenfalls unter Verwendung radikalischer Initiatoren ist bekannt und umfangreich beschrieben. Erläuterungen finden sich beispielsweise in DE 2361743, DE 2513253, DE 2614674, DE 2619969 und DE-A 19524181.Compounds such as styrene, optionally using free radical initiators, are known and have been extensively described. Explanations can be found, for example, in DE 2361743, DE 2513253, DE 2614674, DE 2619969 and DE-A 19524181.
Es ist bekannt, Polymerisationen im Rührkessel oder in anderen Reaktoren, die Mischeinbauten zur Durchmischung und zur Wärmeabfuhr vorweisen, durchzuführen. Dies ist beispielsweise in der DE 2361743 in den Beispielen offenbart. Ein solches Verfahren kann sich jedoch bei Reaktionen, bei welchen viel Reaktionswärme zu- oder abgeführt werden muß als schwer durchführbar erweisen. Ein weiterer Nachteil dieses Verfahrens ist es, daß mit zunehmenden Umsatz die Monomerkonzentration zurück geht und damit die Reaktionsfähigkeit erheblich verringert wird.It is known to carry out polymerizations in a stirred tank or in other reactors which have mixed internals for thorough mixing and for heat dissipation. This is disclosed, for example, in DE 2361743 in the examples. However, such a process can prove difficult to carry out in reactions in which a large amount of heat of reaction has to be added or removed. Another disadvantage of this method is that the monomer concentration decreases with increasing conversion and thus the reactivity is considerably reduced.
Desweiteren sind Reaktoren bekannt, die mit statischen Misch- und Kühleinrichtungen querschnittfüllend ausgerüstet sind. Diese sind beispielsweise in der EP-B 0755945 beschrieben. Diese sogenannten statischen Reaktoren werden als Schleifenreaktoren betrieben, d.h. ein Teil der Polymerisatlösung wird mit dem Zulauf gemischt, während ein anderer Teil aus dem Reaktor entnommen wird und in einem nachgeschalteten Rohrreaktor als Propfenströmung weiter auspolymerisiert wird. Dieses Verfahren gestaltet sich apparativ aufwendig.Furthermore, reactors are known which are equipped with static mixing and cooling devices to fill the cross section. These are described, for example, in EP-B 0755945. These so-called static reactors are operated as loop reactors, i.e. part of the polymer solution is mixed with the feed, while another part is removed from the reactor and polymerized further in a downstream tubular reactor as a plug flow. This process is complex in terms of equipment.
Der Erfindung lag die Aufgabe zugrunde, ein Verfahren zur kontinuierlichen Herstellung von Polymeren aus vinylaromatischen Verbindungen durch Masse- bzw. Lösungspolymerisation zu finden, welches den Einsatz eines relativ preiswerten Reaktors eröffnet und welches eine verfahrenstechnisch einfache und effektive Durchführung der Polymerisation ermöglicht.The object of the invention was to find a process for the continuous production of polymers from vinylaromatic compounds by bulk or solution polymerization, which opens up the use of a relatively inexpensive reactor and which enables the polymerization to be carried out simply and effectively.
Demgemäß wurde ein Verfahren zur kontinuierlichen Herstellung von Polymeren aus vinylaromatischen Verbindungen durch Masse- bzw. Lösungsmittelpolymerisation gefunden, welches dadurch gekennzeichnet ist, daß man die Einsatzstoffe in einen Spiralschlangen- Wärmetauscher führt und dort umsetzt. Spiralschlangen-Wärme- tauscher sind in ihrem Aufbau bereits bekannt und beispielsweise in der Firmenschirft der Fa. KÜHNI-AG Allschwil-Basel "Schlangenkühler bzw. Spiralschlangenverdampfer" beschrieben. Bei dem erfindungsgemäßen Verfahren wird der Spiralschlangen-Wärme- tauscher modifiziert und als Polymerisationsreaktor eingesetzt.Accordingly, a process for the continuous production of polymers from vinyl aromatic compounds by bulk or solvent polymerization has been found, which is characterized in that the starting materials are passed into a spiral coil heat exchanger and reacted there. Spiral snake heat Exchangers are already known in their structure and are described, for example, in the KÜHNI-AG Allschwil-Basel company "snake cooler or spiral snake evaporator". In the process according to the invention, the spiral coil heat exchanger is modified and used as a polymerization reactor.
Die bei dem erfindungsgemäßen Verfahren durchgeführte Polymeria- tion verläuft stark exotherm. Die Rohre des Spiralschlangen-Wärmetauschers werden hierbei vorteilhafterweise mit einem Wärme- Übertragungsmedium wie beispielsweise Diphyl®, Dowtherm S® oder ähnliche wärmebeständige Flüssigkeiten zur Abführung der Reaktionswärme durchflössen. Durch die spiralförmige Anordnung der Rohre ist eine grosse Wärmeaustauschfläche gegeben, wobei das Rohrvolumen am Gesamtvolumen des Reaktors in der Regel 10 % nicht übersteigt. Somit eröffnet das erfindungsgemäße Verfahren eine effektive und wirtschaftliche Wärmeabfuhr und bietet die Möglichkeit, den Polymerisationsprozeß verfahrenstechnisch gut beherrschbar durchzuführen.The polymerization carried out in the process according to the invention is highly exothermic. The tubes of the spiral coil heat exchanger are advantageously flowed through with a heat transfer medium such as Diphyl®, Dowtherm S® or similar heat-resistant liquids for dissipating the heat of reaction. The spiral arrangement of the tubes provides a large heat exchange surface, the tube volume in the total volume of the reactor generally not exceeding 10%. The process according to the invention thus opens up an effective and economical heat dissipation and offers the possibility of carrying out the polymerization process in a manner which is easy to control in terms of process engineering.
Die Rohre innerhalb des Spiralschlangen-Wärmetauschers sind so angeordnet, dass sie im Abstand von etwa 5 bis 15 cm, bevorzugt 8 bis 10 cm, besonders bevorzugt etwa 9 cm über den Reaktorquerschnitt angeordnet sind. Zur besseren Wärmeabfuhr an der Behälterwand kann dieser mit einem Doppelmantel oder mit Halb- schalen versehen werden. Der Doppelmantel bzw. die Halbschalen werden vom selben Wärmeübertragungsmittel wie die Rohre durchflössen.The tubes within the spiral coil heat exchanger are arranged such that they are arranged at a distance of approximately 5 to 15 cm, preferably 8 to 10 cm, particularly preferably approximately 9 cm above the reactor cross section. For better heat dissipation on the tank wall, this can be provided with a double jacket or with half-shells. The double jacket or the half-shells are flowed through by the same heat transfer medium as the pipes.
Zur Steuerung der Reaktionsbedingungen ist der Spiralschlangen- Wärmetauscher bevorzugt in 2 bis 6 Segmente aufgeteilt, die unabhängig voneinander mit kühl- und heizbarem Wärmeträgermedium durchflössen werden.To control the reaction conditions, the spiral coil heat exchanger is preferably divided into 2 to 6 segments, which are flowed through independently of one another by heatable and coolable heat transfer medium.
Dadurch ist gewährleistet, dass durch geeignete Temperaturwahl einerseits eine enge Molekulargewichtsverteilung und andererseits eine ausreichende Fliessfähigkeit der Polymerlösung bei steigendem Umsatz eingestellt werden kann. Die Temperaturwahl hängt von den jeweiligen Rahmenbedingungen ab und kann von dem Fachmann durch Routineversuche ermittelt werden. Aus technischen Gründen kann es vorteilhaft sein, mehrere Spiralschlangen-Wärmetauscher hintereinander zu schalten.This ensures that, on the one hand, a suitable molecular temperature distribution and, on the other hand, sufficient flowability of the polymer solution can be set with increasing conversion by suitable choice of temperature. The choice of temperature depends on the respective general conditions and can be determined by the expert through routine tests. For technical reasons, it can be advantageous to connect several spiral coil heat exchangers in series.
Bevorzugt werden die Einsatzstoffe sowie eventuelle Additive dem Spiralschlangen-Wärmetauscher von unten zugeführt. Bevorzugt wird der hydraulisch gefüllte, d.h. vollständig gefüllte Reaktor in einer Pfropfenströmung von unten nach oben durchflössen. Die Polymerlösung kann direkt ohne Zwischenschalten einer Austrag- spumpe der Entgasungsapparature zugeführt werden.The feed materials and any additives are preferably fed to the spiral coil heat exchanger from below. The hydraulically filled, ie completely filled, reactor is preferably flowed through from bottom to top in a plug flow. The Polymer solution can be fed to the degassing equipment directly without interposing a discharge pump.
Das erfindungsgemäße Verfahren eignet sich bevorzugt für die kon- tinuierliche Herstellung von Polymeren aus vinylaromatischenThe process according to the invention is preferably suitable for the continuous production of polymers from vinylaromatic
Verbindungen, insbesondere Styrol. Als Einsatzstoffe wird hierbei Styrol in Anwesenheit eines Lösungsmittelgemisches enthaltend Styrol/Ethylbenzol verwendet. Weiterhin können Additive wie Mineralöl, Zinkstearat und Farbmittel zugefügt werden. Die Poyme- risationsreaktionen sind beispielsweise im Kunststoffhandbuch 4 "Polystyrol" Carl Hansen Verlag Kapitel 3 "Herstellung von Polystyrol" ausführlich beschrieben.Compounds, especially styrene. Styrene is used as the starting material in the presence of a solvent mixture containing styrene / ethylbenzene. Additives such as mineral oil, zinc stearate and colorants can also be added. The polymerisation reactions are described in detail, for example, in the plastics manual 4 "Polystyrene" Carl Hansen Verlag Chapter 3 "Production of Polystyrene".
Die Reaktion wird bei Temperaturen von etwa 120 bis 180°C bevor- zugt bei 130 bis 170°C und bei Drücken von 1 bar bis 20 bar, bevorzugt 5 bis 10 bar durchgeführt. Der Umsatz des erfindungs- gemäßen Verfahrens wird bevorzugt bis zu etwa 85 Gew. -% durchgeführt. Es kann sich auch empfehlen, den Umsatz bis zu etwa 90 Gew. -% durchzuführen.The reaction is carried out at temperatures of about 120 to 180 ° C., preferably at 130 to 170 ° C. and at pressures of 1 bar to 20 bar, preferably 5 to 10 bar. The conversion of the process according to the invention is preferably carried out up to about 85% by weight. It can also be advisable to carry out the conversion up to about 90% by weight.
Die einfache Verfahrensführung und die Verwendung eines preiswert zu fertigenden Spiralschlangen-Wärmetauschers führen dazu, daß das erfindungsgemäße Verfahren eine wirtschaftliche und verfahrenstechnisch einfache Herstellung von Polymeren aus vinylaroma- tischen Verbindungen durch Masse- bzw. Lösungspolymerisation ermöglicht. Die bei solchen Reaktionen anfallende, hohe Wärmeenergie kann mittels des Spiralschlangen-Wärmetauschers leicht und effektiv abgeführt werden.The simple procedure and the use of an inexpensive spiral coil heat exchanger mean that the process according to the invention enables economical and process-technically simple production of polymers from vinyl aromatic compounds by bulk or solution polymerization. The high thermal energy generated in such reactions can be easily and effectively dissipated using the spiral coil heat exchanger.
BeispieleExamples
Die Versuche wurden in zwei in Serie geschalteten Reaktoren mit je 2 separaten Heiz- und Kühlkreisen gefahren. Die Kühlkreise wurden mit flüssigem Wärmeträgeröl beheizt bzw. gekühlt. Das ge- samte Volumen eines Reaktors beträgt 10 Ltr.The tests were carried out in two reactors connected in series, each with 2 separate heating and cooling circuits. The cooling circuits were heated or cooled with liquid heat transfer oil. The total volume of a reactor is 10 liters.
Dem Reaktor wird eine Lösung aus Styrol und Ethylbenzol, bestehend aus 62 Gew.-% Styrol und 38 Gew. -% Ethylbenzol, bzw. 86 Gew. -% Styrol und 14 Gew. -% Ethylbenzol in einer Menge von 1 bis 2 kg/h zugeführt.A solution of styrene and ethylbenzene, consisting of 62% by weight of styrene and 38% by weight of ethylbenzene, or 86% by weight of styrene and 14% by weight of ethylbenzene in an amount of 1 to 2 kg / h fed.
Der Polymergehalt am Ausgang des Reaktors betrug je nach Zulauf - Zusammensetzung, Temperatur und Verweilzeit zwischen 48 Gew. -% und 80 Gew. -%. Die Polymerlösung wurde anschließend einem Flashverdampfer zum Abtrennen der flüchtigen Bestandteile zugeführt. Die Viskosität - zahl des Polymerisats wurde gemäß DIN 53726 bestimmt.Depending on the feed composition, temperature and residence time, the polymer content at the outlet of the reactor was between 48% by weight and 80% by weight. The polymer solution was then fed to a flash evaporator to remove the volatiles. The viscosity number of the polymer was determined in accordance with DIN 53726.
Beispiel 1example 1
Die Styrolkonzentration betrug 62 Gew. -%, die Polymerisationstemperatur 140°C und die Verweilzeit 20 Std.The styrene concentration was 62% by weight, the polymerization temperature was 140 ° C. and the residence time was 20 hours.
Es wurde ein Polymergehalt von 53 Gew. -% erreicht. Die Viskositätszahl betrug 58 ml/g.A polymer content of 53% by weight was achieved. The viscosity number was 58 ml / g.
Beispiel 2Example 2
Die Styrolkonzentration betrug 62 Gew. -%, die Polymerisationstemperatur 140°C und die Verweilzeit 10 Std.The styrene concentration was 62% by weight, the polymerization temperature was 140 ° C. and the residence time was 10 hours.
Es wurde ein Polymergehalt von 45 Gew. -% erreicht. Die Viskositätszahl betrug 61 ml/g.A polymer content of 45% by weight was achieved. The viscosity number was 61 ml / g.
Beispiel 3Example 3
Die Styrolkonzentration betrug 86,5 Gew. -%, die Polymerisations - temperatur 140°C und die Verweilzeit 10 Std.The styrene concentration was 86.5% by weight, the polymerization temperature was 140 ° C. and the residence time was 10 hours.
Es wurde ein Polymergehalt von 73 Gew. -% erreicht. Die Viskositätszahl betrug 62 ml/g.A polymer content of 73% by weight was achieved. The viscosity number was 62 ml / g.
Beispiel 4Example 4
Die Styrolkonzentration betrug 86,5 Gew. -%, die Polymerisations - temperatur 130°C in der ersten Hälfte und 140°C in der zweiten Hälfte der Polymerisation und die Verweilzeit betrug 20 Std.The styrene concentration was 86.5% by weight, the polymerization temperature 130 ° C. in the first half and 140 ° C. in the second half of the polymerization, and the residence time was 20 hours.
Es wurde ein Polymergehalt von 80 Gew. -% erreicht. Die Viskositätszahl betrug 77 ml/g. A polymer content of 80% by weight was achieved. The viscosity number was 77 ml / g.

Claims

Patentansprüche claims
1. Verfahren zur kontinuierlichen Herstellung von Polymeren aus vinylaromatischen Verbindungen durch Masse- bzw. Lösungs- mittelpolymerisation dadurch gekennzeichnet, daß man die Einsatzstoffe in einen Spiralschlangen-Wärmetauscher führt und dort umsetzt.1. A process for the continuous production of polymers from vinylaromatic compounds by bulk or solvent polymerization, characterized in that the starting materials are introduced into a spiral coil heat exchanger and reacted there.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Einsatzstoffe von unten in den Spiralschlangen-Wärmetauscher einführt.2. The method according to claim 1, characterized in that one introduces the starting materials from below into the spiral coil heat exchanger.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Rohre innerhalb des Spiralschlangen-Wärmetauschers in etwa parallel angeordnet sind und einen Abstand von 5 bis 15 cm aufweisen.3. The method according to claim 1 or 2, characterized in that the tubes are arranged approximately parallel within the spiral coil heat exchanger and have a distance of 5 to 15 cm.
4. Verfahren nach Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß man die Reaktion bei einer Temperatur von 120 bis 180°C durchführt. 4. Process according to Claims 1 to 3, characterized in that the reaction is carried out at a temperature of 120 to 180 ° C.
PCT/EP2000/002709 1999-04-09 2000-03-28 Method for continuously producing polymers WO2000061644A1 (en)

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DE19915916.5 1999-04-09
DE1999115916 DE19915916A1 (en) 1999-04-09 1999-04-09 Process for the continuous production of polymers

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7514147B2 (en) 2003-01-14 2009-04-07 Sabic Innovative Plastics Ip B.V. Formable thermoplastic multi-layer laminate, a formed multi-layer laminate, an article, and a method of making an article
WO2017058385A1 (en) 2015-09-29 2017-04-06 Exxonmobil Chemical Patents Inc. Polymerization using a spiral heat exchanger

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10322830A1 (en) 2003-05-19 2004-12-09 Tesa Ag Process for the continuous production of polymers from vinyl compounds by bulk or solvent polymerization

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1170309A (en) * 1966-12-14 1969-11-12 Plastugil Improvements in or relating to a Process for the Continuous Bulk Polymerization of Styrene
FR2389641A1 (en) * 1977-05-04 1978-12-01 Bayer Ag
EP0755945A1 (en) * 1995-07-26 1997-01-29 Sulzer Chemtech AG Process and device for carrying out a polymerisation in a tube reactor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1170309A (en) * 1966-12-14 1969-11-12 Plastugil Improvements in or relating to a Process for the Continuous Bulk Polymerization of Styrene
FR2389641A1 (en) * 1977-05-04 1978-12-01 Bayer Ag
EP0755945A1 (en) * 1995-07-26 1997-01-29 Sulzer Chemtech AG Process and device for carrying out a polymerisation in a tube reactor

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7514147B2 (en) 2003-01-14 2009-04-07 Sabic Innovative Plastics Ip B.V. Formable thermoplastic multi-layer laminate, a formed multi-layer laminate, an article, and a method of making an article
WO2017058385A1 (en) 2015-09-29 2017-04-06 Exxonmobil Chemical Patents Inc. Polymerization using a spiral heat exchanger
US9708428B2 (en) 2015-09-29 2017-07-18 Exxonmobil Chemical Patents Inc. Polymerization using a spiral heat exchanger
US11279775B2 (en) 2015-09-29 2022-03-22 Exxonmobil Chemical Patents Inc. Polymerization using a spiral heat exchanger

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