DE1767354C3 - Reactor for the continuous implementation of chemical reactions - Google Patents

Description

50

The invention relates to a pin reactor for the continuous Carrying out chemical reactions, which consists of an inner pipe section with con

Oanter form and Q ^ "" ^^^ '^ Separators with about the 8'e.chen Quenwhnat w « jas tube, which moves the interior of the tube Unit scenes for the Re.kt.onsm. hay under ta-ies, a separator magazine for introduction, the Separators in the reactor of the referHc: h ^ de ^^ Separators a closed circle bidet one ^ n.eu se that have a facility to import the Separators and at least one first toned Quantities of

condition ^u ^
it is

gi ΐηΤηΤΪ E _ß ^{e is} _the throughput of the n, the subtracted ε or the reaction w. This is _{what is called} an open type. di T lll

actuators of this type p simultaneously with each other

_{> w} «~ differs significantly from usually only small product quantities in the laboratory or in the techo

. _n . For such purposes

casual reactors of the so-called ie no, ".. enable outside, or also so-called semi-closed type, intermittent or periodic stoicausiaus" during the implementation. allow from outside. In these reactors, the operating conditions are not constant. lh. they are constantly changing, at least * the concentration

^ - Open, continuously operating reactors preferred in industry, of course, because they allow s.ch to be exploited more economically and Automation. However, their uses are less versatile than the closed ones or semi-closed, "which gives the operating personnel the possibility of 1] to intervene at any point and at any point in the reaction and this to steer in oer gcwm. ^. th way. In this way you can, for example, the operating conditions, the temperature, the pressure, the concentration and the like. change add new reactants or subtract part or all of the reaction products. That is at complex reactions are extremely important and the reaction-related selectivities, Operating modes and the reaction kinetics Kecni.u .. «to carry and an optimal flow of the studied chemical reaction in the desired

g ^ SSi important in certain chemical _h ^ ^it _{Reaktionenf such.} B. in polymerizations or analogous reactions, e.g. B. in the polycondensations and polyadditions, in which by appropriate design of the reaction on the shape of the end product and its step-like structure can be influenced in accordance with a previously drawn up plan. In this way it is possible. To produce products to which indi- ^^ Ä, can be conferred by e during the reaction. T ^ ^e £ _{kt for} continuous

* t '% on ^ chemical reactions are

_{There are also ready} s tubular reactors _interior space by movable ^ _is , _{so are} for example in the

p 3148 037 and 22 99 307 Rea-

USA- ^^^. ^. ^ _{Transit of che} .

Reactions described that come from a mnemc constant shape and transverse

movable separators with about

w ^ _id R _{h ht di d}

Inner space of the tube in movable unit cells for raw materials, such as solvents, reactants, the reaction medium, a separator, catalyst, etc., the discharge or return magazine for introducing the separators into the reaction in the circuit of certain products, the tor, the with respect to the separators, a closed change in the reaction conditions, for example, forms a circuit, a lock which is equipped with a device 5 for the temperature, the removal of products and for the introduction of the separators and at least one of the measurement of certain process parameters, first reactants, devices for through Adherence to suitable distances between the intervention introduction of the other reactants, intervention devices from the reactor inlet can also be determined for influencing the reaction and at least the point in time at which certain devices for removing the reaction procedure are carried out should. The good reproductions exist. The known reactors show that the process sequences can be reduced, but they also do not allow a seal between the reactor - an automation of the individual interventions,
entrance and the reactor exit. A reaction results from the fact that the reaction according to the invention under pressure and / or the feeding or tor the advantages of the continuously operating open discharge of reactants or reaction mixture 15 reactors with the advantages of the discontinuous along the pipe section is therefore with the known operating closed or semi-closed reactors difficult or impossible. The task of the reactors combined in itself, with each unit cell invention it is now to be considered a new reactor for the closed type as a small reactor of the closed or semi-continuous implementation of chemical reactions. These indicate that the advantages of the reactors of the 20 unit cells go through successively and continuously open type, in particular their simplicity and, of course, a cycle, passing the stationary economy, with those of the reactors of the attached intervening devices, of the closed or semi-closed type. in particular they are subject to discontinuous treatment, their adaptability and variability, in
unites. as According to a preferred embodiment of the invention

The invention relates to a reactor for manure, the reactor has a lock, which consists of a

continuous implementation of chemical reac- nem block with one or more with seals

Functions of the type described above, the longitudinal bores provided thereby is formed in which

is characterized in that the outlet of the reactor slide with cylindrical pistons, the opposite of which

the input is connected by a separator magazine 30 overlying end faces each one hemispherical

zin made from a tube with a larger internal cavity that is the same diameter

cross section than the cross section of the separators as the separators.

according to a further preferred embodiment

gates from the reactor end to the reactor inlet of the invention consists of the tube of the reactor

in the order given, with the sluice 35 straight sections passing through curved sections

a seal between the two reactor parts are connected to each other, in which Ab / uys- and

with respect to the reactants. Introductory devices are arranged.

According to a further preferred embodiment, the function of the reactor forming the subject of the invention is based essentially on two of the invention, the separators in the reactor have principles, namely the subdivision of the reaction 4 "a spherical or cylindrical shape,
space by separators into discrete unit cells, movable within the and triggers the desired reaction to strip off the reaction tube and thereby trigger storage only inside the reactor.
You can avoid the conditions of intervention on the reagents in the immediate vicinity of the walls of the various stations along the reaction tube, and ensure that the change at certain intervals, so that the entire contents of the tubular reactor at the same time to manufacture several different products according to the type, which are to be mixed with one another on a conveyor belt at stationary intervening devices. So one can be led past. In this way it is possible. For example, according to a certain previous fcst reactions, the plan previously only feasible in the laboratory, the catalyst concentration or the, in particular under reproducible and equal concentrations of one or the other reaction-like conditions, as they have so far only changed in the laboratory participant in order to be in the successive difficult it was possible to carry out polymers with different linearity cells on an industrial scale. It is particularly possible with this. Properties, e.g. B. various average mole polymers or copolymers made to measure in kulargewichten to obtain. Successive large quantities in a fully automatic way, as in the case of unit cells, can be changed periodically in order to produce polymers with various processes in the known continuous large-scale production. This is possible by ^{working in 60} molecular weight ranges in order to obtain separate, measured amounts of reactants by mixing them into a polymer with a molecular weight distribution contained in mobile unit cells which are a desired distribution curve and which together with the separating Se- corresponds .

move parators through a stationary reaction tube. Analogous effects can be achieved in this way.

In doing so, they run to stationary intervention devices 65 that certain parts of the Rcaktionsmcdiums

over, the preprogrammed work processes to the possibly with other parts of the reaction

Carry out reactants within the unit cells, mediums in combination leads to the so

for example, the introduction of certain components, the molecular weight distribution of the

to broaden kromolcküle. It is also possible, in particular, to use liquid for heating or cooling others in the case of anionic polymerization, which allows molecules to circulate. The various addition points or kulargewichlsvcrtciliing by adding catalyst intermediate stations are expediently located in the or stopper vary. Elbows.

The reactor according to the invention is in particular 5 The separators are appropriately spherical, what Can be used for polymerizations or mixed polymers, allowing them to roll in the tube as the re-energizations of unsaturated monomers, e.g. B. exercise for rolling separators is less than for glei -ethylene, Propylene, butylene, butadiene, isoprene, styrene tend (e.g. cylindrical) separators. Besides that and methyl methacrylate, as well as all higher homo- this allows the passage with the lowest possible lies including their halogen derivatives. * ° clearance due to the semicircular pipe elbow.

Of course, one can use the various usual reaction systems, preferably their density is approximately the same, e.g. B. the polymerization like that of the reaction medium to give them a possible mass, in solution, in suspension, in emulsion with low buoyancy and to avoid the corresponding initiator and catalyst systems, the contact or stop zones on the men. However, it is advisable to work to localize the pipe wall in a homogeneous 15. For this purpose, the liquid phase, the gaseous reaction part using hollow spheres, the z. B. present dissolved by Verschwcinehmer or monomers in a solvent ßen of metal hemispheres with a suitable wall thickness or are liquefied under pressure. getting produced. The separators can of course be operated within a wide temperature and pressure range in the reaction medium, which is chemically inert material, in particular by consisting. Of course, you can also provide a spherical shape other than the special one in each cell during the reaction process, e.g. B. a cylindrical shape optionally curved in the center of the reactor with a variable temperature profile; the separators can be applied. In contrast, you can also be provided with sealing members only one from one end to the other of the reactor, such as. B. the sealing rings on the pistons of and thus from the beginning to the end of the reaction 25 internal combustion engines,
set decreasing pressure curve. The margin between the separators and the

The pressure difference to be set between the reactor inlet and the Reak inner wall of the pipe, ie the difference in pressure can, for. B. see the radii of their cross-sections, is preferably achieved by means of pumps, which are small at the entrance and is, for example, of the order of magnitude and at intermediate stations inject the reaction medium by one or two hundredths of the inner diameter or by means of an outlet regulating the outflow Rohrs. Absolute tightness is not required of the step valve. One can also borrow in place of pumps. The relative tightness should be better if the hydrostatic pressure is used, which is inclined from the higher the level of the pipe to the horizontal than the pipe and the lower the flow rate storage containers are supplied. 35 speed of the reaction medium. The experience hai

Preferably, the outlet valve is shown to the pressure that for each value of the clearance set between the inlet of the tubular reactor, to keep the separators and the inner wall of the tube, constant for this pressure and the pressures and each value of the viscosity of the flowing medium! To stabilize the flowing quantities at each point of the reaction and for each inclination of the pipe a minimum gate, so that the setting of a speed of 4 ° of the flowing medium exists, to enable uniform operation before each point, borrowed from the relative speed of the separator . becomes zero compared to the flowing medium. Sc

If the flow rates are stabilized, which is, for example, in the case of horizontal velocities, the residence time of the tube, which contains a liquid with the same viscosity reaction medium uniformly, with all parts of the reaction medium as water , and in the case of spherical reaction medium, the same treatment cycle Separators, the diameter of which is subject to 99% of the inside. diameter of the pipe is the minimum speed

According to a preferred embodiment, the speed 1 to 5 cm / sec for pipe diameters between the circle formed by the pipe is designed so that 10 and 500 mm. In practice, it is advisable to reduce the pressure height and to reduce the pressure drop to a higher circulation speed, which is very long in relation to the diameter of the pipe, especially around the critical area, so that both sides of a separator and accidental fluctuations take into account and in his vicinity to wear the prints as practically the same. Speeds in the order of magnitude can be viewed. from 1 to 10 times the diameter of the pipe prc

According to a further preferred arrangement, 55 seconds are generally suitable, especially when the tubular reactor consists of almost horizontal clearance between the inner wall of the tube unc arranged parts and the separators have about cm to two hundredths of the separators, preferably one of the Density of the reaction medium is the inner diameter of the tube, approximate density. The distance between consecutive sepa

Generators according to a particularly simple and cheap ⁶ °, and consequently the total number of the same arrangement is the tubular reactor of a temporarily existing separators can vary within wide bundle of tubular, straight and of equal length TEI limits vary. Preferably, a large number of unit cells and separators is used approximately horizontally and parallel to one another. Layers are arranged one on top of the other at slightly different levels, but without the length of each unit cell, these pipe parts by 65, for example, less than the I of ache of the pipe by means of semicircular pipe elbows connected to one another. As a rule, one achieves good results. Each tube is in a second, results with unit cells with a length between heat-insulated envelope, in which one is to 10 and 200 times the pipe diameter.

YV

The connection according to the invention between the curves in FIGS. 14 and 15, which shows the relationship between the end of the tubular reactor and its beginning between the average styrene content of a mixing agent in a lock, is expediently designed to reproduce an outlet opening for the reaction, depending on the degree of conversion,
medium under pressure and an entry opening for 5

at least one of the fresh reaction medium Fig. I schematically illustrates the reactor of the invention

having bildcndcn flowable media under pressure. application in z. B. on a mixed polymer

these openings being the end or the beginning of the sation of styrene and butadiene in solution in heptane

Form reactor. The seal between the reacts by means of a butyllithium catalyst.

torcingang and its output is indicated by an i ° 1 denotes a tubular container, the

perforated seal causes the separa- at an input 2 and via a pipe 3 to a

be able to cross gates by means of a sluice. Lock 4 is connected. This tubular loading

According to a preferred arrangement, the holder contains a spherical separator 6 in

inner capacity of the lock exactly the discrete amounts of 5 subdivided reaction medium.

Volume of a separator so that no reaction 15 The container 1 is surrounded by double jackets 7,

medium can be carried. each having an inlet 8 and an outlet 9

Various devices can be used to separate and around the pipe 1 a flowable medium allow passage through the seal. Regulating the temperature of the ent-fin in this tube first system can circulate reaction medium held by two coaxial cylinders. the exist, which without any leeway due to the separation «subdivision of the double jackets 7 into different walls can slide, each cylinder in a cut allows the adjustment of the temperature of the its end faces a hemispherical hollow reaction medium along its entire path. Entraum with the same diameter as the separa- long of this path are a certain number of has goals. By means of straight movements, intermediate stations can be provided, which are continuously ardiese both cylinders on one side of the gasket * 5.

take a separator, move it to the other side The lock 4 is connected to an inlet 11 for under pressure

transport and release there again. Hydrau- incoming flowable medium connected that

Lische piston cylinder or any other suitable z. B. the solvent containing the monomers

System can be the rectilinear movements of the one. At a first intermediate station 12 there

and'or the other of the two cylinders 3 ° the catalyst is ensured by means of a metering pump 13

Afford. sator too.

Another preferred system consists of min- At a second intermediate station there is a

at least one of the two cylinders with its mixture by the reaction medium by means of a

to press the hollow end face against the seal, the pump 16 and a bypass line 17 at 14

has an opening, the diameter of which sucks the through 35 and is ejected again at 15. Simultaneously

a separator occurs. The two cylinders are driven by the pump 19 at 18 z. B. Catalyst

thus ensure alternately a dense supply or additional monomers are supplied.

End and a passage opening for the Sepa- At a third intermediate station 20 is a part

rator. "" of the reac-

The invention is subsequently returned to the cycle with the aid of the medium.
Drawings which illustrate the device and a fourth intermediate station 23 v is explained in more detail by means of an exemplary embodiment of the reactor.
for reactions carried out according to the invention and of course, the reaction can be accelerated or described as the products obtained. 45 slow down by changing the temperature from

one section of the reaction tube to the other

In the drawing shows increased or decreased.

F12. I a schematic representation of an inventively- Finally, the reaction medium is through the

according to the reactor, * " ^{with the pipe 3} connected line 25

FIG. 2 shows a perspective illustration of an invented 50 removed.

according to the reactor with the lock scheme The various spherical separators ί

table is represented by a parallelepiped. are from the circulating reaction medium

3 shows a cross-sectional view of the tube bundle carried along. In doing so, their distance increases, if

according to Fig. 2 ^eme addition takes place and it is reduced when off

Fig. 4 is a longitudinal section through a straight line 55 is pulled off the container somewhat. Tube part The diameter of the balls themselves is roughly the same 5 shows a longitudinal section through a curved inner diameter of the pipe. In the pipe 3 However, the pipe part takes the pipe diameter based on 6 shows a plan view of a lock. the point 26 to, so that the pipe from then on Fig. 7 forms a longitudinal section through a lock 6 ° magazine for separators to the through a

along the line VII-VH of Fig. 6, accumulation of separators-related pressure

Fig. 8 a cross-sectional view of a sluice - do not increase loss,

long the line VIH-VIII of Fig. 7. The lock consists of a with a Langsboh-

Fig. 9 shows a cross section through a lock along tion 27 provided block in the two pistons 28 and

the line 1X-1X of FIGS. 7 and ⁶ S "g""tcn. The hole 27 is on one side with de,

Fig. 10 to 13 molecular weight distribution curves of inlet opening 11 and the inlet 2 of the tubular

of m.gen container obtained in Examples 1 to 4 below, and on the other hand with the

d_i ·. ^r outlet 25 and the pipe 3 of the container in connection

ίο

manure. This hole is closed in its center by the seal 30, which has an opening 31 with a diameter corresponding to the separators 6. The end faces of the pistons 28 and 29 each have a hemispherical cavity 32 and 33, the diameter of which is approximately the same as that of the separators 6; these cavities are surrounded by a bearing surface 34 or 35 in such a way that they can lie tightly against the seal 30 . The pistons 28 and 29 also each carry an ejector 36 b / w. 37, which is elastically mounted on a piping 38 or 39 in order to eject the ball 6.

Each of the pistons 28 and 29 can slide in the bore 27, its movement for example by hydraulic device, not shown, is controlled.

When the piston 28 is brought up to the seal 30 , it ensures the separation between points 2 and 3. When the piston 29 is far enough away from the partition wall 30, a separator 6 carried along by the reaction flow enters the bore 27. If the piston 29 then moves onto the seal 30 / u, it grips the separator 6, practically without entraining liquid, and, as it strikes the seal 30, it in turn ensures the separation between points 2 and 3. The piston 28 can then slide back, whereby the separator 6 is released and carried along by the reaction stream. Of course, seals 40 and 41 allow pistons 28 and 29 to slide in bore 27 in a sealed manner. The transfer of a separator 6 from the pipe 3 to the inlet 2 can be controlled, for example, by means of a clockwork drive or when a separator passes through a certain point in the circuit, e.g. B. exit 26.

FIGS. 2 to 5 explain an embodiment en> reactor according to the invention.

The reactor here consists of a tube arrangement which is formed from a series of straight tubes 50. Each tube is surrounded by a double jacket 51 which is provided with an inlet 52 and an outlet 53 for a heat exchange medium. Each tube has a stationary flange 54 at each of its ends with a movable flange 55. Two successive tubes connected by a curved, U-shaped element ending in two stationary flanges 61 can be screwed together at the movable flanges. In the flanges 61 threaded bores 62 are provided, in which one can screw either a plug or a connection to an injection or discharge pump. As FIG. 3 shows, the pipes on each floor do not have the same height. Rather, a slight slope of, for example,] ° / in the direction of the circuit is provided so that the curved pieces 60 have a height difference between their ends in order to facilitate the passage of the balls 6 in these curved pipe parts. It is sufficient for this purpose to arrange the tubes on supports 65 by means of blocks 66 which are provided at the downstream end of each tube.

From FIG. 2, on the other hand, the input 2 is »that Tube 3, the lock 4, as well as the main inlet 11 for flowable medium and the discharge 25 can be seen.

The last tube 67 is the only one with a considerable incline, which must also be machined so precisely on the inside that the clearance between its inner wall and the separators is so small that the separators are carried along despite the upward inclination. However, with increasing! Viscosity of the reaction medium at the end of the reaction, the change in viscosity is sufficient to entrain the separators through the rise of the pipe.

In Fig. 2, an inlet 12 for additional liquid and a single intermediate injection point 15 is shown

ίο represents.

Figures 6-9 show a sluice made with a "tubular container such as that shown in Figures 2 through f is shown works satisfactorily.

The lock essentially consists of a block 100, which has various transverse and longitudinal bores and a vertical bore. The transverse bores 101 and 102 , which are arranged one above the other, serve to pass the flowable media bil denden the reaction medium, one side of the inlet 2 and the other the tube 3 forms. The purpose of the lock is to enable the transition from balls from the bore 101 to the bore 102 while simultaneously separating the two circuits zi.

The upper bore 101 is connected to the pipe 103, which forms the end of the tubular reactor, and to the pipe 104 , which forms the outlet end for the flowable media and is connected to the outlet valve.

The lower bore 102 is connected to the pipe 104a forming the inlet 1 of the reactor and to the pipe 105 forming the inlet 2 of the tubular reactor.
The lock also has two identical resistors arranged longitudinal bores 110 and 111, which the transverse bores 101 and 102 at right angles to meet in each of these holes to slide piston 113, 114, 115 and 116. At the meeting point of the Bohrunger 101 and 110 and the bores 102 and 111 are ir

4 ″ the bores 110 and 111 cylindrical grids II and 118 are provided, which allow the passage of flowable media, but hold back the balls 119 and 120.
Inflatable seals 121, which hold ge by means of rings and are connected to the inlets for pressurized flowable media, enable the pistons to slide tightly with little friction. The two pistons 113 and 115 on the one hand and 1 and 116 on the other hand are fastened to flanges 130 and 131 by means of screw bolts I3i, the flanges in turn being connected to the shafts 133 and 134 in front of hydraulic cylinders 135 and 136. Pistons 113 and 114 have opposite end faces, each with a hemispherical shape

gene cavity 137, the diameter of which is approximately the same as that of a separator, so that when eir Separator 119 is taken between the two pistons, together with the separator only a minimal « Amount of liquid trapped in this cavity

will. The pistons 113 and 114 are also provided with an ejection system consisting of an ejector 138 Spring 139 and a screw nut 140 screwed into a central thread 141.

The lock is finally vertical with a

Bore 150 provided, which connects the two bores 110 and 111. This hole is with a Pipe 151 for the inlet of washing liquid for you Separators and a pipe 152 for the discharge,

2f

connected to this liquid wedge. The tube 152 opens into an intermediate sleeve 153 which is closed with a plug 154 which is extended by a central shaft 155 and whose vertical position is adjusted by means of a handwheel 156.

As FIG. 9 shows, a transverse bore 160 which is closed by two glass plates 161 and 162 held by means of frames 163 and 164 screwed onto the block 100 enables the processes taking place in the vertical tube 150 to be observed.

Whether the entirety of the fixed elements constituting the lock, in particular the block 100 and the piston / ylinder 135 and 136, is mounted on a fixed frame 142 , which is made up of one another by means of screws. There is rivets or welded profile particles.

The way this lock works is easy to understand. After their stay in the reactor, the flowable media arrive at the distributor 100 and pass through it through the pipe 103, the bore 101 and the pipe 104. The separators, on the other hand, are held up by the grid 117 . If it is desired to transfer a separator 119 held up by the grid 117 , the hydraulic piston cylinders are acted upon in such a way that the pistons 113 and 114 approach one another and grip the spherical separator. Then they are moved apart again so that the separator is fed to the vertical bore 150 , whereupon the separator falling into the bore 150 is released, whereby it is always washed with the washing liquid circulating in the tubes 151 and 152.

The separator is then stopped by the stem 155 of the plug 154 and gripped by the pistons 115 and 116. A sliding movement then leads the separator to the bore 102, where it is carried along by the medium flowing in the tubes 104 and 105.

Experience has shown that a tubular reactor, as has been described with reference to FIGS. 2 to 9, functions perfectly and can easily be adapted to various polymerizations or other reactions. Nevertheless, one should observe some precautionary measures when starting up. So it is inexpedient to equip the device and the system of distributing the separators with an inert flowable medium, e.g. B. pure solvent or solvent laden with monomers to set in motion. The setting is easier if you first start the reaction and then distribute the separators. In this latter case, a first approximation of the value of the viscosity of the reaction medium, as it should be along the entire length of the pipe, is obtained. In the former case, ie with an inert medium, on the other hand, the viscosity is very different from that of the medium during the reaction.

The following examples are intended to show what you can do can achieve with the reactor according to the invention. They were shown with one in the drawing Reactor carried out, which the following numerically expressed properties owned:

Volume of the tubular container 901 Inner diameter of the tubes 24 mm Length of the individual tubes 6 m Total length 200 m

Diameter of spherical

Separators 23.8 mm

Distance between each two

Separators Im

Total throughput ... . about 45 l / h, i.e. H. 2 h

Dwell time

Inlet pressure 8 to 10 kg / cm-depending on

the trials pressure difference
ίο between the

Entry and

Outlet 3.5 to 4 kg / cm ² for one

Liquid with an average viscosity of about 10 poise

Temperature changeable along the

tubular container. Linear speed 2.7 cm / sec

example 1

At the inlet of the reactor, 40 l / h of heptane and 4.6 l / h of butadiene are added under a pressure of 10 kg / cm * to.

Then, in the same way, a few meters from the inlet end, butyllilhium is introduced in an amount of 0.055 % {] ", ', corresponds to 1 part by weight of catalyst per 100 parts by weight of monomer. The temperature is kept at 50 ° C. over the entire length of the reactor. The solution of the polymer obtained is treated with antioxidants and chain terminators in the last sections of the reactor. and the polybutadiene obtained has an intrinsic viscosity of 2.35 with a Mooney plasticity of 50. Its microstructure is as follows:

1—2: 10.5 ",,
1-4 trans: 50 ",,
\ -4 ice: 39.5 ° _Λ ,

The molecular weight distribution is shown by the curve labeled 1 in FIG. For VcrJ same purposes 10 are in Fig., The curve 2, the MoIeJ kulargewichtsverteilung of under the same conditions in the laboratory in small bottles with einerr capacity of 250 cm ³ obtained polymers, and the curves denoted by 3 and 4 give the molecular weight distribution of polymers wel before they were obtained in a continuously operating vat reactor with the same catalyst system and with approximately the same average reaction time and the same dosages.

As can be seen, the polymer obtained by the method according to the invention , although el was produced by a continuous process , resembles a polymer produced in the laboratory in a discontinuous process. Its distribution is even narrower.

Example 2

The procedure is as in Example 1, except that 4.6 l / h of butadiene is introduced at a point of 4.6 l / h of a mixture of 23% styrene and 77% butadiene. At the same time m

13 14

the Bjtyllithium introduced in an amount of 0.04% (for definition see Bei- ie at a distance from the inlet end according to I) is given 0.010% corresponding to 20% of the length of the reactor,
Hexamethylphosphortriamid and causes a ^ _le third, consisting of 0.028% butyllilhium mixing by suction and subsequent _{un (} j 0.08% HMPT, calculated on the initial pushing back with increased speed by means of 5 monomers, with a conversion of 60%, <L h. a centrifugal pump. the pressure at the inlet end of _me i _nem distance from the inlet end in accordance with amounts to 8 kg / cm *, the temperature is on the whole 330, <j _he Länee of the reactor.
Maintained at 30 ° C. The resultant mixed with antioxidants and chain terminators. The residence time is 2 hours, as in the other solutions is collected at the outlet end. 10 examples. The pressure at the input endc is

In this example, the conversion is also 8 kg / cm ² . The temperature between the first and the

almost 100%. The intrinsic viscosity is 1.65, the second catalyst injection is 35 ° C, between the

Mooney plasticity of the polymer is 48. The microsecond and third 27 ° C and after the third up to

structure is as follows: addition of antioxidant and chain terminator

, _ · ,. _{sn <} 1/15! "tad 30 ⁰ C.

_ ~ '\ -. A τ; »/ ^{That at the end with a degree of} conversion of

■ ^ai | _4 · is »almost 100% obtained polymer possesses an intrinsic

^CIS "she viscosity of 2.15 and a Mooney plasticity

In Fig. 11, the curve labeled 1 gives that of 60. Its molecular weight distribution is a we-

Molecular weight distribution of the polymer obtained is slightly broader than that of the polymer from Example 3.

sats on. Curves 2 and 3, respectively, give the molecular as shown by the curve of FIG. Though his

Weight distributions of in an analogous manner, but Mooney-Plastiz did the same as that of the polymer

with 30 and 18% styrene, respectively, instead of 23% obtained from Example 3, its intrinsic viscosity is higher.

Polymers. Curve 4, on the other hand, indicates that any number of polymers can be used with the same

Molecular weight distribution as in the case of omitting 25 plasticity, but with higher intrinsic viscosities

the separators in the reactor was obtained and than in the usual processes, or even polymers

curve 5 shows those under the same conditions with the same intrinsic viscosity, but one

moles obtained in a conventional open reactor - greater plasticity, d. H. a low index of

weight distribution. Mooney plasticity. produce.

Example 3 Example 5

The above example is repeated, but in this example a butadiene / styrene mixture

with the exception that the catalyst and the polymer with a statistical distribution of the two

Hexamethylphosphoric triamide (HMPT) can be obtained in two por- 35 monomers in the chains, namely

admits. In a first phase you give 0.013% without using a polar compound such as Te-

(See Example 1 for definition) butyllithium and 0.036% trahydrofuran or hexamethylphosphoric triamide

HMPT / u and works at 35X. (HMPT).

In a / long phase after the reaction, 40 l / h of heptane is introduced at the top of the reactor,

Has reached 48%, i.e. H. at an approximate distance of 40 0.735 l / h styrene and 0.960 l / h butadiene. Then there

from the starting point, the 20% of the length of the pipe, a 0.045% (for definition see example I), is calculated

corresponding to the size of the reactor, 0.045% of butylnet is added to the total of the intended monomers

lithium and 0.08% 'HMPT, based on the amount (4.6 l / h), the corresponding amount of butyllithium. the

of starting monomers and lowers the Tcnipe pressure at the inlet end is 8 kg / cm ² and the

temperature to 30 C. 45 temperature is set along the entire length of the container

The polymer obtained has a curve kept at 60 ° C. The content of the mixture is regulated

from I ig. 12 shown bidisperse molecular weight polymers of styrene so that the percentage

distribution. Its properties are: styrene of the polymer forming 55% not

Degree of conversion exceeds 100%, and as soon as you get this percentage

intrinsic viscosity 2 ⁵ ° ^errelcht <g ^{| bt you elne} further amount of butadiene to.

w ™ ρ ♦ £ ', -, u \ ^{One leads one} after the other 0.6 l / h; 0.48 l / h; 0.375 l / h:

Mooney Plastmtat 60 _{a2g5 | / h;} ^ ₃₅ , _{/ h and} ^ ₈₅ ^ ^ J ^ ^ ^

The copolymer obtained has a distance from the inlet end of the reactor

Properties similar to Example 2, but offers II or 2 or 3 or 4 or 5 or 6 sevenths of the dei

Advantage of easier processability. 55 reactor length.

After these six butadiene additions, the average composition of the mixed poly

Example 4 merisats 22% styrene, its content of l-2 structure slightly;

Proceed as in Examples 2 and 3, ^{using 10} % ^and the conversion of the monomeric styrene:

however, three catalyst ^injections on: 6o occurred to 80%.

,. . ,, "",,. At this point the polymer can be used

the first with a conversion of 0 / d. . _{(] by adding more ßutadiei in} several layers

close to the entry end; this consists of 0.012% „, ^„ Γϋ!, ™. In this case the salary remains ar

nni ""'u1, Dx ^P ° ^{Blltylllthlum and} l-2 compoundsctwal0%.

U.OJG, / "HMII. 6 _{5 You can also put the rest of the butadiene on cinma}

add the second consisting of 0.015% butyllithium, d. H. a quantity of 0.775 l / h and 0.10 "

and 0.045% HMPT calculated on the incorporated HMPT (calculated on the total amount of mono

set monomers, with a conversion of 44%, kidney). In this case one avoids the education

15 16

a styrene block and the macromolecules have an amount of monomers, too. The composition of the

their ends are a statistical sequence of the two mono- unreacted monomers from then to zi

mers with 22% styrene. In this latter case, 100% implementation statistically possesses,

the polymer obtained has an intrinsic viscosity of The curve of the instantaneous compositions

1.9, a Mooney plasticity of 50 and a content of 5 of the copolymers (proportion of styrene) is shown in FIG. Ii

of compounds with a 1-2 structure of 18%. This is indicated in the same way as in Fig. 14; di <

The profile of the instantaneous styrene content is the solid curve in the curve gives the instantaneous content ar

of FIG. 14, which shows the percentage content of styrene. and the dashed curve gives the mean

Styrene of the polymer formed is reflected in a given styrene content of the copolymer formed

Moment of the reaction, depending on the environmental ¹ O The copolymer obtained has the following

shows degree of settlement of the monomeric styrene. the properties:

Example 6 intrinsic viscosity 1.70

_{T,. n} ....... , ... "_ ·, Mooney plasticity 57

In this example we want to use the distribution of _{content in} j.2 connections 29 ° /

of the monomers (butadiene and styrene) in the chains _contain 15 trans-1-4 compounds. 47%

and on the other hand on the microstructure, especially the transition temperature in the vitreous

the content of 1-2 compounds, act like this _{state ω dnej} . _Warmth . _Diffe .

in French patent specification 15 19 743 special analysis - 54 ° C
ben is.

The reactor is charged under a pressure of 20 The curves corresponding to the examples are given

of 10 kg / cm ² hourly with 40 liters of heptane, 0.75 liters of styrene again:

and 2,661 butadiene. \ j-j ΐ> ·· ι> ι_ *. j

In addition, 0.035% (see Example 1 for definition) ^a > ^d I ^{e the} £ ^IS P ^lcIe "', ^bis , ⁴ corresponding curve

Butyllithium and 0.025% Hexamethylphosphortri- ^{1 to} J, ^{13 d 'M e} °' f. ^ku ! ^ar J ^e 7ί ^ ίϋ '"" ^ **

amide (HMPT), calculated on the total amount of an * 5 ^st ' ^{mmt according to the method of} gel penetration

Monomers (4.6 l), too. chromatography

B is carried out at a temperature of 6O ⁰ C.) which Examples 5 and 6 corresponding Kurver

Since the amount HMPT for achieving a grain nd 14 _U 15 the percentage of in the mixing

plexes with the butyllithium is not sufficient, has polymer-bound styrene, determined by

the copolymer which then forms does not have a complete measurement of the refractive index, depending on the wedge

statistical distribution and accumulates in styrene, depending on the degree of conversion of the mono used

however, it has a low content of 1-2 compounds (styrenes).
fertilize.

After running through the reaction path to ¹ I ₃ As the above examples show, enables

the remainder butadiene is added, d. H. hourly the reactor according to the invention a design of the

1.28 1. Since the composition of the mono-polymerization and the resulting polymer *

changes, from this point on it changes continuously and in a simpler way than a ge

forming copolymer is richer in butadiene. closed reactor. The number of possible

After ⁷ / e of the reaction path have gone through, operations is almost unlimited and indeed sub

give 0.050% HMPT, calculated on the total * o application of relatively simple means.

In addition 7 sheets of drawings

Claims (4)

Patent claims: flow of the reaction and at least one device I. Reactor for the continuous implementation of chemical reactions, consisting of a inner pipe section with constant shape and cross-sectional area, using movable separators has roughly the same cross-section as the tube, which divides the interior of the tube into movable unit cells for the reaction medium, a separator magazine for introducing the separators into the reactor, which is related to the Separators form a closed circuit, a sluice with a device for introducing the separators and at least one first reactant is equipped, means for Introducing the other reactants, intervention devices for influencing the reaction and at least one device for withdrawing the reaction product, thereby marked ao indicates that the exit (26) of the reactor is connected to the input (2) by a separator magazine, which consists of a tube (3) with a larger internal cross-section than the cross-section of the separators (6), and one Lock (4) for transferring the separators (6) from the reactor end (26) to the reactor inlet (2) in the order given, with the sluice (4) creating a seal between these two Reactor parts (2, 26) caused with respect to the reactants. 2. Reactor according to claim 1, characterized in that the lock (4) is formed from a block with one or more longitudinal bores (27; 110, 111) provided with seals (30, 121) , in which cylindrical pistons (28, 29; 113 , 114) slide whose opposite end faces each have a hemispherical cavity (32, 33; 137) which has the same diameter as the separators (6). 3. Reactor according to claim 1, characterized in that the tube consists of straight sections which are connected to one another by curved sections in which trigger and introduction devices are arranged. 4. Reactor according to Claims 1 to 3, characterized in that the separators (6) are spherical or have a cylindrical shape.