AU706258B2 - Process and apparatus for performing a polymerisation in a tube reactor - Google Patents
Process and apparatus for performing a polymerisation in a tube reactor Download PDFInfo
- Publication number
- AU706258B2 AU706258B2 AU60666/96A AU6066696A AU706258B2 AU 706258 B2 AU706258 B2 AU 706258B2 AU 60666/96 A AU60666/96 A AU 60666/96A AU 6066696 A AU6066696 A AU 6066696A AU 706258 B2 AU706258 B2 AU 706258B2
- Authority
- AU
- Australia
- Prior art keywords
- tube reactor
- mixture
- polymerisation
- heat exchanger
- monomer
- 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
Links
- 238000000034 method Methods 0.000 title claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 12
- 239000007858 starting material Substances 0.000 claims description 12
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002959 polymer blend Polymers 0.000 claims description 2
- 235000009917 Crataegus X brevipes Nutrition 0.000 claims 1
- 235000013204 Crataegus X haemacarpa Nutrition 0.000 claims 1
- 235000009685 Crataegus X maligna Nutrition 0.000 claims 1
- 235000009444 Crataegus X rubrocarnea Nutrition 0.000 claims 1
- 235000009486 Crataegus bullatus Nutrition 0.000 claims 1
- 235000017181 Crataegus chrysocarpa Nutrition 0.000 claims 1
- 235000009682 Crataegus limnophila Nutrition 0.000 claims 1
- 235000004423 Crataegus monogyna Nutrition 0.000 claims 1
- 240000000171 Crataegus monogyna Species 0.000 claims 1
- 235000002313 Crataegus paludosa Nutrition 0.000 claims 1
- 235000009840 Crataegus x incaedua Nutrition 0.000 claims 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims 1
- 239000004926 polymethyl methacrylate Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- MQFGFMVFKVUOOF-UHFFFAOYSA-N potassium;1,9-dihydrofluoren-1-ide Chemical compound [K+].C1=C[C-]=C2CC3=CC=CC=C3C2=C1 MQFGFMVFKVUOOF-UHFFFAOYSA-N 0.000 description 1
- IRAPFUAOCHNONS-UHFFFAOYSA-N potassium;phenylmethylbenzene Chemical compound [K+].C=1C=CC=CC=1[CH-]C1=CC=CC=C1 IRAPFUAOCHNONS-UHFFFAOYSA-N 0.000 description 1
- ZYBHSWXEWOPHBJ-UHFFFAOYSA-N potassium;propan-2-ylbenzene Chemical compound [K+].C[C-](C)C1=CC=CC=C1 ZYBHSWXEWOPHBJ-UHFFFAOYSA-N 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/2435—Loop-type reactors
-
- 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
- C08F2/02—Polymerisation in bulk
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (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)
- Physical Or Chemical Processes And Apparatus (AREA)
Description
P.6691 Ehph Sulzer Chemtech AG, Winterthur, Switzerland Process and apparatus for performing a polymerisation in a tube reactor The invention relates to a process for carrying out a polymerisation in a tube reactor. It also refers to an apparatus for carrying out the process as well as to corresponding uses.
Polystyrenes and copolymers, polyacrylates such as PMMA and other products can be polymerised by means of ionic initiation. This initiation is brought about by anionic or cationic starter substances which are mixed into the monomer.
Such starter substances, called starters for short, are temperature sensitive and decompose if the temperature exceeds, for example, 150 0
C.
Metal-organic compounds known as starter substances are: sec butyl-lithium
(C
4 HgLi) and cumyl-potassium (CgHnK) for the manufacture of polystyrene, diphenylmethyl-potassium
(C
13
H
11 fluorenyl-potassium
(C
13
H
9 K) and lithium chloride (LiCI) for the manufacture of polymethylmethylacrylate (PMMA) 2 The ionic polymerisation is rapid and highly exothermic. Due to the heat liberated the temperature can increase to beyond the decomposition temperature of the starter, whereupon the reaction ceases.
In order to carry out a continuous reaction, it is proposed to use a tube reactor in which the static mixer elements are arranged to be cross section filling (cf. EP 0 096 201).
Since, however, the polymerisation is associated with a strong increase in viscosity, problems arise which can lead to non-uniform product quality. As a result of the axial viscosity gradient a segregation can develop in which strongly polymerised, highly viscous phases can separate out from the less polymerised phases of lower viscosity in the mixture. Furthermore, the formation of a deposit on the reactor walls can also contribute to insufficiency of the product quality.
oo It is thus the object of the invention to provide a continuous process for the ionic polymerisation which leads to an improved product quality. This object is satisfied by the features of claim 1. In this process the axial viscosity gradient in a tube reactor is compensated for by a returned reaction product which still consists of unreacted monomers to a considerable extent. In order to prevent polymerisation from occurring in the return line, which would have a disturbing influence on the carrying out of the process, the starter is thermally annihilated at the outlet of the reactor.
The dependent claims 2 to 4 relate to advantageous embodiments of the process in accordance with the invention.
Claims 5 to 7 relate to apparatuses for carrying out the 3 process in accordance with the invention, and claim 8 relates to corresponding uses.
In the following the invention will be explained on the basis of the drawings. Shown are: Fig. 1 a schematic representation of the installation for carrying out the process in accordance with the invention, and Fig. 2 a diagram with the schematically represented plot of the temperature and the viscosity in the installation of Fig. 1 e* -The scheme of Fig. 1 shows: a tube reactor 1, a mixer-heat exchanger 2 for heating the product, a pump 3, a mixer-heat exchanger 4 for cooling the mixture to be fed into the reactor 1, a supply point 5 for a monomer M, a supply point 6 for a starter S and a removal point 7 for the product produced in accordance with the invention. The temperature and viscosity values are shown in the drawing of Fig. 2 for two embodiments for the points A, B, C and D.
The solid curves 10 (temperature) and 20 (viscosity) are associated with the first embodiment. The product P contains equal parts of polymer and monomer, namely 2.7 kg/h of each.
At point D, 26.4 kg/h of this polymer-monomer mixture leaves the heat exchanger 2. Of this, 21.6 kg/h is returned via the pump 3 to point A, where 5.4 kg/h of monomer M is admixed.
The temperature of this mixture is 124 0 C at A. The temperature is lowered to 100 0 C in the cooler 4 between A and B. Thereafter, starter S is admixed at B. In the reactor tube 1 the temperature rises due to the liberated reaction heat to 4 126 0 C (point By heating in the heat exchanger 2, the temperature of the product is finally raised to 150 0 C. At this temperature the starter S decomposes. As the curve shows, the viscosity increases in the reactor 2 between B and C from 0.78 to 2.37 Pa s (Ns/m 2 that is approximately threefold.
Whereas in the first exemplary embodiment the degree of transformation ratio of the amount of the monomer to the total amount) increases from 40 to 50 during the reaction, provision is made in the second example dashed curves 11 and 12 that the degree of transformation increases from to 50 Here the viscosity in the reactor 1 increases from 0.064 to 1.097 Pa s, i.e. by about a factor of 17. This ratio is disadvantageously high; it should preferably not be greater than As the curve 12 for the second exemplary embodiment shows, **9 the product would just have the decomposition temperature 9* (150 0 C) after the reactor if no cooling took place between A and B. In this case the cooler 4 and the heater 2 could be dispensed with. It is however not recommendable to provide this special execution of the process, since, on the one hand, a large increase in viscosity is present and, on the other hand, it would be difficult to carry out a control of the process.
For a given mixing ratio of returned product and freshly introduced monomer an initial temperature is preferably provided by the heat exchanger 4 in such a manner that the temperature of the mixture at the outlet of the tube reactor lies at least 5 K below the decomposition temperature.
5 The tube reactor 1 advantageously has mixer elements whose structure is built up of intermeshing arms which cross one another, with the arms forming two groups of structure elements aligned in parallel (cf. DE-PS 28 08 854).
For the mixer-heat exchangers 2 and 4 an apparatus is preferably chosen as known from DE-PS 28 39 564: This apparatus is a static mixer with arms which are executed as heat exchanger tubes.
6 THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 1. Process for carrying out a polymerisation in a tube reactor comprising the following steps: mixing a freshly introduced monomer with a returned monomer-polymer mixture as well as cooling the mixture to a prescribed initial temperature, admixing an inactivatable polymerisation starter, the inactivation of which begins when heated above a decomposition temperature, as well as performing a partial polymerisation in the tube reactor, heating the mixture leaving the tube reactor to at least the said decomposition temperature, and finally returning a portion of the mixture and removal of the other portion as product.
2. Process in accordance with claim 1 characterised in that at least half of the mixture at the outlet of the tube reactor is present in polymerised form.
3. Process in accordance with claim 1 characterised in that the amount of the returned mixture is chosen in relation to the amount of monomer introduced in such a manner that the viscosity of the mixture in the tube reactor during polymerisation does not increase by more than approximately a factor of ten.
4. Process in accordance with claim 1 characterised in that for a given mixing ratio of returned mixture and freshly introduced monomer an initial temperature is prescribed so that the temperature of the mixture at the outlet of the tube reactor lies at least 5 K below the decomposition temperature.
5. Apparatus for carrying out the process in accordance with claim 1 comprising the following components: a tube reactor with static mixer elements arranged so as to be space filling, at least one mixer-heat exchanger 2) at each of the input side and the
Claims (3)
- 6. Apparatus in accordance with claim 5 characterised in that the tube reactor has mixer elements with a structure which is built up of arms crossing and intermeshing with one another, where the arms form two groups of structure elements directed parallel to one another.
- 7. Apparatus in accordance with claim 5 characterised in that the mixer-heat exchangers 4) are static mixers with arms which are formed as heat exchanger tubes.
- 8. The apparatus according to claim 5 for the manufacture of polystyrene or PMMA, where sec-butyl-lithium or LiCI respectively is used as an ionic starter. DATED this 28th day of August 1998 SULZER CHEMTECH AG WATERMARK PATENT TRADEMARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA DOC 23 AU6066696.WPC IAS/CLR/CC P.6691 Ehph Abstract of Disclosure The process for carrying out a polymerisation in a tube reactor comprises the following steps: Freshly introduced monomer is mixed with a returned monomer-polymer mixture. The mixture is cooled to a prescribed initial temperature (heat exchanger A polymerisation starter which is inactivatable upon heating above a decomposition temperature is admixed. A partial polymerisation takes place in the tube reactor. The mixture leaving the tube reactor is heated up to at least the said decomposition temperature (heat exchanger Finally, a portion of the mixture is returned (pump 3) and the other portion removed as product (Fig. 1) 0 «n.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95810486 | 1995-07-26 | ||
| EP95810486A EP0755945B1 (en) | 1995-07-26 | 1995-07-26 | Process and device for carrying out a polymerisation in a tube reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU6066696A AU6066696A (en) | 1997-01-30 |
| AU706258B2 true AU706258B2 (en) | 1999-06-10 |
Family
ID=8221777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU60666/96A Ceased AU706258B2 (en) | 1995-07-26 | 1996-07-24 | Process and apparatus for performing a polymerisation in a tube reactor |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5602216A (en) |
| EP (1) | EP0755945B1 (en) |
| JP (1) | JPH0940704A (en) |
| AU (1) | AU706258B2 (en) |
| CA (1) | CA2181633C (en) |
| DE (1) | DE59504339D1 (en) |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2768740B1 (en) * | 1997-09-19 | 2001-07-06 | Bp Chem Int Ltd | CONTINUOUS POLYMERIZATION PROCESS OF A VINYL MONOMER |
| ATE219701T1 (en) | 1998-04-28 | 2002-07-15 | Univ Heriot Watt | METHOD AND DEVICE FOR PHASE-SEPARATED SYNTHESIS |
| DE19915916A1 (en) * | 1999-04-09 | 2000-10-12 | Basf Ag | Process for the continuous production of polymers |
| CN1555387A (en) | 2000-07-28 | 2004-12-15 | 古德里奇公司 | Polymer composition for producing an optical waveguide, optical waveguide produced therefrom and method for producing the waveguide |
| US6906164B2 (en) | 2000-12-07 | 2005-06-14 | Eastman Chemical Company | Polyester process using a pipe reactor |
| WO2002046266A2 (en) * | 2000-12-07 | 2002-06-13 | Eastman Chemical Company | Low cost polyester process using a pipe reactor |
| 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 |
| PT1542793E (en) | 2002-09-23 | 2007-09-17 | Total Petrochemicals Res Feluy | Slurry loop polyolefin reactor |
| EP1410843A1 (en) * | 2002-10-17 | 2004-04-21 | ATOFINA Research | Slurry loop polyolefin reactor |
| 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 |
| US7135541B2 (en) | 2003-06-06 | 2006-11-14 | Eastman Chemical Company | Polyester process using a pipe reactor |
| US7074879B2 (en) * | 2003-06-06 | 2006-07-11 | Eastman Chemical Company | Polyester process using a pipe reactor |
| US7332548B2 (en) * | 2004-03-04 | 2008-02-19 | Eastman Chemical Company | Process for production of a polyester product from alkylene oxide and carboxylic acid |
| JP4068108B2 (en) * | 2005-11-04 | 2008-03-26 | 大陽日酸株式会社 | Heating medium heating and cooling device |
| US20100105847A1 (en) | 2006-01-24 | 2010-04-29 | Intertape Polymer Corp. | Plug flow bulk polymerization of vinyl monomers |
| US7906598B2 (en) * | 2006-08-30 | 2011-03-15 | Intertape Polymer Corp. | Recirculation loop reactor bulk polymerization process |
| WO2008027858A1 (en) * | 2006-08-30 | 2008-03-06 | Intertape Polymer Corp. | Recirculation loop reactor bulk polymerization process |
| US20080139780A1 (en) * | 2006-12-07 | 2008-06-12 | Debruin Bruce Roger | Polyester production system employing short residence time esterification |
| US7649109B2 (en) * | 2006-12-07 | 2010-01-19 | Eastman Chemical Company | Polyester production system employing recirculation of hot alcohol to esterification zone |
| US7943094B2 (en) | 2006-12-07 | 2011-05-17 | Grupo Petrotemex, S.A. De C.V. | Polyester production system employing horizontally elongated esterification vessel |
| US7863477B2 (en) | 2007-03-08 | 2011-01-04 | Eastman Chemical Company | Polyester production system employing hot paste to esterification zone |
| US7868129B2 (en) * | 2007-07-12 | 2011-01-11 | Eastman Chemical Company | Sloped tubular reactor with spaced sequential trays |
| US7868130B2 (en) * | 2007-07-12 | 2011-01-11 | Eastman Chemical Company | Multi-level tubular reactor with vertically spaced segments |
| US7847053B2 (en) * | 2007-07-12 | 2010-12-07 | Eastman Chemical Company | Multi-level tubular reactor with oppositely extending segments |
| US7872090B2 (en) * | 2007-07-12 | 2011-01-18 | Eastman Chemical Company | Reactor system with optimized heating and phase separation |
| US7858730B2 (en) | 2007-07-12 | 2010-12-28 | Eastman Chemical Company | Multi-level tubular reactor with dual headers |
| US7842777B2 (en) * | 2007-07-12 | 2010-11-30 | Eastman Chemical Company | Sloped tubular reactor with divided flow |
| US7829653B2 (en) * | 2007-07-12 | 2010-11-09 | Eastman Chemical Company | Horizontal trayed reactor |
| US7872089B2 (en) | 2007-07-12 | 2011-01-18 | Eastman Chemical Company | Multi-level tubular reactor with internal tray |
| DE102007040850A1 (en) | 2007-08-29 | 2009-03-05 | Wacker Chemie Ag | Process for the preparation of protective colloid-stabilized polymers and apparatus for carrying out the process |
| JP2014012781A (en) * | 2012-07-05 | 2014-01-23 | Sumitomo Chemical Co Ltd | Method for producing methacrylic polymer composition |
| CN103333278B (en) * | 2013-01-30 | 2016-02-24 | 衢州市鼎盛化工科技有限公司 | A kind of device and technique thereof preparing fluoropolymer and fluorinated copolymer |
| RU2607916C1 (en) * | 2015-12-21 | 2017-01-11 | Владимир Леонидович Письменный | Heat exchanger |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2808854C2 (en) | 1977-05-31 | 1986-05-28 | Gebrüder Sulzer AG, 8401 Winterthur | Flow channel provided with internals for a medium involved in an indirect exchange, in particular heat exchange |
| DE2839564C2 (en) | 1978-09-12 | 1982-10-21 | Hoechst Ag, 6000 Frankfurt | Device with supply and removal of heat and for mixing liquid media |
| US4324868A (en) * | 1979-06-19 | 1982-04-13 | Mitsubishi Rayon Co., Ltd. | Process and apparatus for preparation of vinyl polymers |
| CH649230A5 (en) | 1982-06-03 | 1985-05-15 | Sulzer Ag | REACTOR FOR THE CONTINUOUS IMPLEMENTATION OF POLYMERISATIONS IN HIGH VISCOSITY MEDIA. |
| US5194525A (en) * | 1988-12-12 | 1993-03-16 | Dainippon Ink And Chemicals, Inc. | Continuous mass polymerization process for making styrene copolymers |
| DE4235980A1 (en) * | 1992-10-24 | 1994-04-28 | Basf Ag | Process for the preparation of a vinyl aromatic compound |
-
1995
- 1995-07-26 EP EP95810486A patent/EP0755945B1/en not_active Expired - Lifetime
- 1995-07-26 DE DE59504339T patent/DE59504339D1/en not_active Expired - Lifetime
-
1996
- 1996-07-19 CA CA002181633A patent/CA2181633C/en not_active Expired - Lifetime
- 1996-07-22 US US08/681,437 patent/US5602216A/en not_active Expired - Lifetime
- 1996-07-23 JP JP8193221A patent/JPH0940704A/en active Pending
- 1996-07-24 AU AU60666/96A patent/AU706258B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| CA2181633C (en) | 1999-12-14 |
| EP0755945B1 (en) | 1998-11-25 |
| CA2181633A1 (en) | 1997-01-27 |
| DE59504339D1 (en) | 1999-01-07 |
| US5602216A (en) | 1997-02-11 |
| EP0755945A1 (en) | 1997-01-29 |
| AU6066696A (en) | 1997-01-30 |
| JPH0940704A (en) | 1997-02-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU706258B2 (en) | Process and apparatus for performing a polymerisation in a tube reactor | |
| JP4410416B2 (en) | Method and apparatus for continuous production of polymer | |
| CA2295654A1 (en) | Process for producing hyperbranched polymers | |
| US3644294A (en) | Process and equipment for the continuous production of polyesters | |
| CA1070897A (en) | Continuous solvent-free polymerisation of vinyl derivatives | |
| TW521078B (en) | Method and apparatus for producing HIPS using continuous polybutadiene feed | |
| DE19638094A1 (en) | Process for the preparation of methyl methacrylate polymers in a circulation reactor | |
| JPH0113726B2 (en) | ||
| EP0486262A1 (en) | Chemical processes | |
| US6488898B1 (en) | Process for preparing acrylonitrile-styrene copolymer | |
| US3639372A (en) | Method for the polymerization of alkenyl aromatic monomers | |
| Szabo et al. | Copolymerization and terpolymerization in continuous nonideal reactors | |
| DE2141770A1 (en) | METHOD AND APPARATUS FOR THE PRODUCTION OF POLYMERIZED OR COPOLYMERIZED BY VINYL CHLORIDE BY CONTINUOUS BULK POLYMERIZATION | |
| US3349070A (en) | Bulk polymerization process | |
| Mejdell et al. | Modelling of industrial S-PVC reactor | |
| Ray | Dynamic behaviour of polymerization reactors | |
| US3503949A (en) | Process for polymerizing gaseous ethylene utilizing a constant diameter reactor with varying surface area/volume ratio | |
| US1915555A (en) | x procbss por the production of thickened oil with | |
| CH649278A5 (en) | METHOD FOR CONTINUOUSLY FORMING AN ACID FLUORIDE FROM CARBON MONOXIDE, WATER-FREE HYDROFLUORINE AND AN OLEFIN. | |
| JPH0977806A (en) | Continuous polymerization method | |
| AU2005201143A1 (en) | A continuous process for preparing polymers | |
| CN108299784A (en) | A kind of resistance to thermal level ABS resin and preparation method thereof | |
| DE3115602C2 (en) | ||
| Lhila et al. | Mixing in Viscous Polymer Reactors | |
| KR830002912B1 (en) | Continuous production method of rubbery methyl methacrylate syrup |