JPS62101608A - Method and apparatus for manufacturing isobutyrene polymer - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the chemistry of polymers, and more particularly to a method and apparatus for producing isobutylene polymers. It has found wide applications in the chemical and petrochemical industries as insulating oils, additives to fuels and oils, ingredients in sealing, adhesives and insulation compositions.

[Prior art]

Currently, the main method for producing isobutylene polymers is based on cationic polymerization of isobutylene-containing feedstocks in the presence of acid catalysts.

As starting feedstock, isobutylene content J~60% by weight
Commercial fractions of C4 hydrocarbons with
70%) is used. As solvents, halogen-containing hydrocarbons (CF2Cl, C2H5C1, etc.) are mainly used.

Polymerization catalysts are individual Lewis acids and complexes based on them (AICI, BF, , C2 used as solutions in organic solvents (C2H5C1, imbutane, toluene).
H3AIC1□, 5nC14).

The isobutylene polymerization method is carried out from -100°C to 1I under strong stirring.
It is carried out at a temperature of ro"c.

The polymerization reaction proceeds rapidly, is exothermic, and involves the release of large amounts of heat (approximately 7 kJ mol).

This intense heat release during polymerization imposes stringent requirements on reaction temperature control. This can be done in a number of ways, namely the action of dilute monomers, the gradual introduction of the catalyst solution, the boiling of a portion of the monomers or specially introduced volatile solvents and the use of the reactor used. (Achieved by thorough heat removal through developed external and internal temperature-regulating surface areas.

The polymerization process for isobutylene-containing feedstocks is based on high capacity (2
~, yo7,1"). Liquid ammonia, ethylene and various antifreeze agents are used as temperature regulators. The reactor has a high heat transfer coefficient and mass transfer. Consists of a tubular or column-type device provided with a powerful stirring device that guarantees the coefficient.In order to control the temperature conditions of the isobutylene polymerization process, it has a free space that guarantees the boiling or evaporation of a part of the monomer or solvent A mixing reactor is used. Process control is also achieved by carrying out the reaction in a series of mixing devices, in which the conversion of the monomers is reached in each individual device. For this reason, / Heat release per unit is reduced. In all cases, high conversions of the starting feedstock are achieved with more than average residence time in the reactor.

These prior art methods of producing isobutylene polymers have the following disadvantages. First and foremost is the high metal consumption of the process associated with the use of heavy duty equipment of complex design. This also implies a need for skilled personnel in the service and maintenance of process equipment. Second,
The presence of a system that provides intense heat and mass transfer during the reaction results in high power consumption. They can be increased non-linearly when increasing the unit capacity of the equipment or in the case of a series of equipment, i.e. schemes intended for better temperature regulation of the process and higher quality of the final product. Ru. Third, despite a number of techniques that attempt to maintain a constant reaction temperature, the process occurs under non-isothermal conditions with a temperature gradient across the volume of the reaction mass. This results in a non-uniformity of the isobutylene polymer with respect to its molecular weight, especially a low molecular weight fraction which impairs the utility of the product.

Fourth, the long residence time (hr) of the starting feedstock in the reactor, which is not reasonably matched with the appropriate polymerization time (sec), limits the productivity of the reactor and prevents the occurrence of side reactions. thus impairing the quality of the product.

Improvements in the process for producing isobutylene polymers allow for a reduction in the metal and power intensity of the process, a more reliable temperature control, while ensuring high yields and high quality of the polymer product.

From this point of view, the production of isobutylene polymers in small-sized tubular reactors is the most promising route. In this way, French patent No. 1. ．． 3q1. ．． /93 specification is,
Steel pipe with a capacity of 0.51 (diameter J~30cm, length 700m)
teaches the polymerization of isobutylene in a C4 cut within a C4 fraction. A special mixer (capacity o, oos l, impeller speed 1,3
The polymerization of the starting feedstock mixed with catalyst C7■5A1c12 at 00 rpm) is carried out in laminar flow (no stirring) at adiabatic conditions (temperature from O''C to -/30 °C). The linear velocity is /~cr/L/sec. This method has the following advantages: simplification of polymerization reactor design, high conversion of isobutylene (close to /θo%)
and has the possibility of producing polyisobutylene with different molecular weights (-7θ00 to several million).

However, despite these advantages, this prior art method has significant drawbacks. Adiabatic conditions do not guarantee the isothermal nature of the process (the temperature drop at the inlet and outlet of the reactor is in the range q~/θθ°C), which leads to high molecular weight heterogeneity, i.e. poor quality. to produce a polymer with

The use of low-productivity mixers of /J% size with feedstock and catalyst in the process scheme is characterized by high economic efficiency, but limits the output of the product from the tubular reactor (on average /per hour/~tl of polymer).

The productivity of the reactor used is also rather low due to limitations in the feedstock composition. The use of fractions with a high content of isobutylene (more than % SO) is not possible due to the significant imbalance between heat release and heat consumption, which interferes with the required bed conditions of the process.

The need to use a powerful cooling source (liquid ethylene) for component pre-cooling imposes severe limitations on process equipment, which makes the process rather complex and poses fire and explosion hazards.

A better parameter for the process is FRG% λ,
This is achieved in the case of the polymerization of isobutylene in a tubular reactor as disclosed in No. 90'l, 3/e.

The polymerization of isobutylene in the composition of the C4 fraction occurs at a linear velocity o
, r to x m in a turbulently moving feed stream at 7 seconds at temperatures from -50°C to +go°C and under pressures up to 50 atmospheres.

As process catalyst BF5 is used in an amount of /~J mmol/mole of isobutylene. Ol, 2 for BF3
The use of co-catalysts (water, alcohol) in amounts of ~7 mol.
acceptable.

The average reaction time was /-1 second and the conversion rate was io.

Close to Chi. The reaction is carried out at a molecular weight soo suitable for the production of additives.
-j, ooo to produce a polymer.

The process is long! continuous in a tubular reactor with x 102 to g x 106 N and a diameter of 10 to 100 Mm, preferably having a helical or coiled shape and placed in a temperature-regulating medium ('0.0-body ammonia); It is carried out according to

This prior art process according to FRG % Patent No. 2,901I, 3/47 has a number of disadvantages. As specified in that patent specification, the isothermal nature of the process is not achieved since a large amount of heat is released at the inlet of the reactor as a result of the polymerization and a gas phase is formed. This increases the pressure at the outlet of the tubular reactor.

Increased pressure results in a higher total resistance of the system. The productivity of the reactor is therefore several hundred kg/hour, which is considerably lower than the calculated theoretical value.

These difficulties extend from longer length to length goowm,
may prove insurmountable in the case of tubular reactors with diameters up to 10θ.

An increase in the length of the reactor at the same time increases the metal consumption for the equipment and increases the power consumption rate for the process, which almost corresponds to the process parameters carried out in complicated high-capacity reactors. This negates the simplicity and other advantages of making isobutylene polymers in tubular reactors.

Said process has the disadvantage that the yield of the desired product is low and never exceeds 70%. The reason is that the non-isothermal nature of the process results in significant amounts of low molecular weight fractions.

The process according to FRG Patent No. 90, No. 3 is also limited with respect to the range of isobutylene polymers produced. The method can only produce products with molecular weights only within the range of 500-5,00θ.

[Problems to be solved]

The present invention provides increased yields of high productivity, broad molecular weight isobutylene polymers in processes carried out in equipment that allows for reduced metal and power consumption of the process equipment in a reduced production floor area. The present invention relates to a process for the production of isobutylene polymers intended for controlled polymerization in high-speed turbulent flow of the reaction mass, which would allow for a controlled polymerization of the reaction mass.

[Means for solving problems]

The purpose of this is to introduce into the reaction zone of the reactor an isobutylene-containing feed stream and a solution stream of acid catalyst with a temperature of -70°C from OoC, followed by a reaction mass stream that moves turbulently along the reactor. In producing isobutylene polymers having molecules f(/30,000 or less) in a tubular reactor by a process consisting of polymerizing a feedstock of 30° to 30° to the axis of the reaction mass stream, into the reaction zone at an angle of 200° and a catalyst solution stream is fed into the reaction zone at at least one point such that the catalyst stream feed direction forms an angle of 30° to 9000° with respect to the feedstock feed direction; This is achieved by a process for the production of isobutylene polymers, which is characterized in that it has a speed of 0.3 to n71/s, a temperature of 0 to 60"C and a pressure of 1 to 5 atm.

For the present invention, the average yield of polymer product is about 90 parts, and the unit productivity is higher than that which can be achieved when carrying out the process according to FRG Patent No. 90Q, 3/H. /
3-～. ! 0 times higher and 10 times higher (total productivity) than that of the method according to the FRG patent. The present invention makes it possible to produce isobutylene polymers with molecular weights in the range of 300 to iso, oθO.

In order to ensure additional temperature control of the process and to provide more favorable conditions for the mixing of catalyst and isobutylene-containing feedstock, according to the invention the temperature of the catalyst solution stream is varied from OoC to -
It is desirable that the qO'C is within the range.

Further, in accordance with the present invention, it is desirable that the catalyst solution be introduced into the reaction zone at a rate that provides a catalyst concentration in the reaction mass of 0.0/~O,S weight.

According to the invention, in order to obtain isobutylene polymers having a molecular weight of 300 to 1,000, the reaction mass stream is
It is also desirable to have a temperature within the range of 40°C.

According to the invention, the molecular weight is 1,100-. To obtain an isobutylene polymer with 20,000
It is also desirable to have a temperature of 10-30°C.

Furthermore, according to the present invention, the molecular weight is 20,000 to iso,
oo.

It is also desirable for the reaction mass stream to have a temperature in the range of 0-10''C in order to obtain an isobutylene polymer having a

An apparatus comprising a tube with separate inlets on one side for the feedstock and the catalyst, the inlet device for the feedstock and the inlet device for the catalyst being made in the form of a socket pipe; the inlet socket vibe for the catalyst being in the form of a socket pipe; oriented inwardly and having at least two openings on its cylindrical surface, the axes of which are at an angle of 300 to 90° to the axis of the tube.
and the socket pipe for feed supply is placed on the cylindrical surface of the tube close to its end face; the length-to-diameter ratio of the tube is varied from m:/ to 100:/; the catalyst inlet The ratio of the length of the socket pipe to the length of the tube is from ノ: YO to l: OO, and the length to diameter ratio of the catalyst inlet socket pipe is 10 to 50:/. In the apparatus, it is desirable to carry out a method for producing an isobutylene polymer having a molecular weight of 15θ, 000 or less.

Due to the use of the device according to the invention, metal consumption is reduced by a factor of 100, and power consumption by 75-20%.

According to the invention, the tube preferably has an additional nozzle fixed to the inlet socket pipe for the catalyst. The nozzle is embodied as two to six metal plates fixed along their length along the axis of the tube and positioned radially at an angle to each other forming a reaction zone with the inner surface of the tube. Ru.

According to the invention, it is also desirable that the socket pipe for supplying the raw material is arranged at an angle of 300 to /000 with respect to the axis of the pipe.

Furthermore, it is desirable that the material supply socket pipe is oriented with respect to the end face of the tube such that its axis is offset with respect to the axis of the tube.

Other objects and advantages of the present invention will become more fully apparent from the following detailed description of a method for making isobutylene polymers and an apparatus for carrying out the method, as well as examples and accompanying drawings illustrating the method. .

[Detailed description of the invention]

The method for producing isobutylene polymers having a molecular weight of less than or equal to isO,000 according to the invention uses, for example, the following composition as the starting isobutylene-containing feedstock: propane l~-wt, propylene o,6~/, 2.3i Amount: Isobutane - SS weight %, n-butylene 71.7 - 3.0 weight %, α-butylene O, a -/Y weight %, isobutylene
~ Otsuo weight section, trans-butylene col Hiromu weight%
, eig-butylene 3-7% by weight, divinyl 9.7-2
This is carried out by using a C4 hydrocarbon fraction with % by weight.

Before use, the starting isobutylene-containing feedstock is pre-rectified to remove resin and mechanical impurities, dried and cooled to a temperature of 0-30°C (ammonia coolant).

As starting isobutylene-containing feedstock, 20-3 oz 6 m of individual isobutylene (99.5% purity) in chlorinated solvent (methylene chloride, ethyl chloride) pre-cooled to a temperature within the range of -30°C to -90°C. It is also possible to use liquids.

The method for producing isobutylene polymers is carried out in the presence of an acid catalyst. As the latter, a solution of aluminum chloride in ethyl chloride or methyl chloride at a concentration of 7 to 3% is suitable.

Solutions of aluminum chloride in mixtures of toluene, xylene and/or aromatic hydrocarbons have a concentration of up to 1Ao. Ethylaluminum dichloride in gasoline, solutions of ethylaluminum sesquichloride in gasoline, solutions of complexes of ethylaluminum chloride with water or alcohol in gasoline have a concentration of /~, V%. Boron trifluoride and its ester are 1, /
−j% concentration.

Prior to use in the method, the solution of catalyst is prepared with ammonia and/or
or cooled with ethylene coolant to a temperature within the range of 0°C to -qo°C.

The starting isobutylene-containing feedstock and catalyst are fed to the reaction zone in separate streams. Their feed direction according to the invention forms an angle of 300 to 900, thus ensuring effective mixing of the flows. Additionally, we have determined that the catalyst solution stream has a catalyst concentration in the reaction mass of
We have found that it should be fed to the reaction zone at at least two points at a rate that ensures ~0.5 weight percent.

As is well known, the provision of highly efficient processes for the production of isobutylene polymers contemplates high speeds of isobutylene-containing feed streams.

According to the invention, the typical flow rate of catalyst and feedstock in the reaction zone is required to be between 0.3 and 1 m7 seconds. This is due to the need to provide a turbulent flow of the reaction mass. The inventors found that turbulence is ineffective for reaction flow rates below 0.3@/sec, while turbulence in the reaction flow is
It has been found that speeds higher than 3m7s reduce conversion. This is explained by the reduction in the effective residence time of the isobutylene-containing feedstock within the reaction zone.

The degree of turbulence equal to about IO according to the invention is evaluated by standard formulas, such as the Reynolds criterion. The minimum value of the Reynolds criterion, calculated from the values of the dynamic factors of medium linear velocity, flow density, viscosity and the diameter of the tube, is equal to approximately lθ4, thus indicating the turbulent character of the flow.

In the method disclosed in FRG Patent No. 2,901/-,317, the use of high linear velocities (up to 20 m 7 seconds) of the reaction mass flow with the turbulent characteristics of the flow does not guarantee high productivity that will correspond to current flow. The gas phase formed within the inlet zone of the reactor is difficult to remove due to the
Increases system resistance.

As a result, despite the set high linear velocity of the flow, the polymer product appears at the exit from the system only after several tens of minutes rather than after a few seconds (as according to simple calculations). Therefore, at the linear velocities described in FRG Patent No. Co, etol I, 3i4c, the inherent high production steady-state characteristics are not achieved. As a result, the FRG% allowance No. 2, 9
The productivity of the process disclosed in No. 014.31II is only about a few hundred kg of polymer/hr, whereas in the process according to the invention the productivity is equal to several tons of polymer/hr.

The effect of the turbulence necessary for carrying out the process according to the invention at a reaction mass flow rate of 0.3 to tsm/s is such that, as already mentioned, the isobutylene-containing feed stream is /
Due to the fact that it is entered into the reaction zone at an angle of 200°.

The high linear velocity of feedstock movement as well as the high speed of the polymerization process meets the need for rapid and efficient production of catalyst and feedstock streams. This requirement is met by feeding a stream of catalyst solution to the reaction zone in the method described above.

The reaction in high-speed turbulent flow is characterized by an immediate decrease in reaction volume due to rapid polymerization of isobutylene and intense heat release due to the exothermic nature of the reaction. In combination,
They cause a sharp increase in flow turbulence and thus favor reaction completion. The heat generated in the reaction is consumed for evaporation of a portion of the feedstock. 0-1.0℃
At a temperature of the reaction stream within the range of / under a pressure of ~5 atm, boiling and effective removal of the heat generated during the reaction are controlled, as well as close to isothermal properties despite the absence of external temperature regulation. Process characteristics (temperature variation across the reaction mass flow is ±
x, y'c).

In the method according to FRG Patent No. 2,904', j/4, near-isothermal polymerization reaction characteristics are not guaranteed. According to this patent, the pressure and reaction temperature are applied to proceed to very high conversions.This technique avoids the possibility of releasing the heat of polymerization reaction by boiling the starting feedstock and creating a temperature difference at the beginning and end of the reaction stream. and thus impairing the quality of the polymer product.

Varying the temperature and pressure of the reaction mass stream within the aforementioned limits, in addition to maintaining process isothermal properties, results in high total conversion of the feedstock (as demonstrated by the inventors).
guarantees the possibility of controlling the properties (molecular weight, molecular weight distribution) of the final product (up to 93%).

The unique feature of the control of the molecular weight properties of isobutylene polymers during polymerization in high-speed turbulent flow lies in the high sensitivity of the process to relatively small changes in temperature and pressure.

Thus, according to the invention, in order to produce isobutylene polymers with a molecular weight of 300 to 100, the reaction mass should have a temperature in the range of 50 to 60C. For the production of isobutylene polymers with molecular weight WOO~i, ooo, the reaction mass flow is /I left~! It should have a temperature within the range of θ°C.

According to the present invention, the molecular weight is 1,000-! In order to produce isobutylene polymers having a molecular weight of 5,000 to io, 000, the reaction mass stream should have a temperature in the range of po -its °C, while isobutylene polymers having a molecular weight of 5,000 to For the production of coalescence, the temperature of the reaction mass stream should be equal to 33°C to 80°C, and the molecular weight 1
For the production of isobutylene polymers with a θ of 0.00 to 20,000, the temperature of the reaction mass should be equal to 30 to 33 °C. According to the invention, the molecular weight +2o
, ooo -so, ooo, the temperature of the reaction mass should be equal to 9-30 °C, and the molecular weight go, ooo ~ 150
,000 isobutylene polymer, the reaction mass should have a temperature in the range of 0 to 3°C.

The method for producing isobutylene polymers according to the invention comprises the steps of preparing a tube/(Figs. figure)
should be carried out in a reactor constructed as The length-to-diameter ratio of this tube is determined for a given linear velocity of the turbulent flow of the reaction mass (0,3~/Sm/s) for reasons of kinetics or reaction duration (equal to a fraction of - seconds). °C to ensure optimum residence time of the components in the reaction zone. Tube length to diameter ratio J
Below :/, acceptable completion of the reaction is not reached, ie the productivity of the apparatus is reduced. A tube length-to-diameter ratio of 100:/> does not have a significant effect on the completion of the polymerization (the monomer conversion is high enough even without it), but the resulting polymer This increases the likelihood of side reactions occurring that impair the quality of the product and unreasonably increase the metal consumption of the equipment.

The tube 1 is a catalyst supply socket pipe provided on the end face of the tube and extending inwardly with respect to the tube (Figs. 1, 2, 3, μ and 3). has. According to the invention, the ratio of vipco length to tube/length is:
/: should be in the range of 5 to 72-00, while the length-to-diameter ratio of the pipe should be equal to 10-/ to 0:/. This condition ensures a uniform distribution of the catalyst within the bulk of the isobutylene-containing feedstock and thus makes it possible to create the necessary turbulence of the flow.

At low ratios (less than 10 9, the catalyst feed socket pipe 2 presents a high hydrodynamic resistance to the feed stream, thus limiting the productivity of the tubular reactor. At higher ratios (less than 150 ), the socket vipco for catalyst supply does not guarantee the required volumetric concentration of catalyst in the reaction zone, i.e. its effective distribution. decrease in sex.

Ratio of linear dimension of tube / to catalyst feed pipe goo from 5: / to 2
00: / is a polymerization process due to the controlled distribution of the catalyst along the feed stream which, in combination with the desired temperature and pressure of the feed stream, ensures the production of polymers with a wide range of molecular weight values and molecular weight distributions. allows you to control. Smaller differences in the linear dimensions of the tube and the catalyst inlet vibe (ratio less than S:1) do not guarantee the isothermal nature of the process (temperature fluctuations greater than ±20.t'c) and result in mainly small molecule production. generate things. Upper limit of ratio value λQO
Exceeding :/ is accompanied by a reduction in the useful space of the tubular reactor/ and an increase in system resistance. This results in disadvantages such as increased metal consumption, higher energy consumption, and difficulty in maintaining stable process conditions, which is totally undesirable.

The absence of a special unit for the introduction of catalyst into the feed stream by the prototype method and equipment is the fundamental reason for the drastic difference in productivity achieved with the method according to the invention and that of the prototype. There are seven of them.

According to the invention, it is preferred that the nozzle 3 is provided on the catalyst socket pipe (FIGS. 9 and S). The nozzles have two to six nozzles positioned radially at an angle to each other, fixed along their length along the axis of the tube, and forming a reaction zone (FIG. 5) with the inner surface of the tube. It is made in the form of a metal plate lI (see left figure). The presence of this nozzle has a favorable effect on the homogeneous distribution of heat and the removal of the heat of reaction from the stream as well as on the polymerization reaction, creating near-isothermal conditions. - It is obvious that a larger number of plates in the nozzle is desirable. However, this number should be limited to six plates, since with a larger number the resistance to the feed stream increases rapidly and the productivity of the reactor is reduced.

According to the invention, the socket vibrator placed in the tube l=
At least one opening 6 (FIG. 1) should be provided on the surface of the tube l, the axis of which is 3 to the axis of the tube l.
00 to 9000 to form an angle α.

Artificial tube 7 for the introduction of isobutylene-containing feedstock placed on the cylindrical surface of the tube near its end face (Fig. 1,
2 and 3) are also provided on the tube l. The angle β of pipe 7 with respect to the axis of pipe / is ? Embodiments of the invention with positioning between 0° and /J0 are also possible (FIG. 1).

Furthermore, according to the invention, the pipe holder is positioned on the pipe/in such a way that the knob 7 is oriented with respect to the end face of the pipe l in such a way that its axis is offset with respect to the longitudinal axis of the pipe/. It is also possible to do so (Figure 3).

We believe that this design ensures a higher degree of turbulence in the reaction bulk flow than so% and thus a more uniform distribution of catalyst within the reaction bulk. It has been found that this facilitates the process and therefore results in higher productivity.

At feedstock introduction angles of less than 30°, a cocurrent flow of feedstock and catalyst is formed which worsens the conditions for catalyst distribution within the feedstream and thus reduces the yield of the final product.

At angles greater than 1,2θ0, the formation of countercurrents forming a dead zone becomes dominant. This means that
resulting in excessive power consumption and lower productivity.

For the purpose of evacuation of the target product, an outlet socket pipe g (
FIG. 1) is provided on the end face of the tube opposite to the end face on which the input socket vipco is positioned.

The device according to the invention works in the following way.

The isobutylene-containing feedstock, cooled to a temperature within the range of 0°C to -90°C, is passed through the inlet socket pipe 7 to 0°C.
．． into the reactor tube/s at a speed of 3 to 15 m/s.

The catalyst solution at a temperature within the range of 0°C to -90°C is fed to the reactor tubes/tubes through an inlet socket pipe in an amount that ensures complete conversion of the monomers and stable operation of the reactor. Ru.

The degree of turbulence of the reaction mass flow and its temperature depend on the inclination angle β of the socket pipe with respect to the axis of the tube/, the deflection of its axis with respect to the axis of the pipe/, as well as the perforation of the socket pipe λ and the pressure of the reaction mass flow. be adjusted. Reactor operating conditions, equipment to record changes in reaction mass flow temperature and pressure, respectively? and 10 (FIG. 1).

The resulting isobutylene polymer is sampled intermittently by a sampler // (FIG. 1) for control of its molecular weight properties.

The final product is discharged from the reactor tube l through the outlet socket pipe g and the subsequent outgassing (outgaa
slng).

[Embodiments of the invention]

Example/~/3 Commercial fractions of C4 hydrocarbons are used for polymerization.

It is Flopyrene 0. A~/2%, Prono-kun/
~ Yuchi, Isobutane Care ~, 11I%, n-butane 1,
3-3%, α-butene 0. II-/T, isobutylene t
Contains to-5S%, β-butylene 0.2-1%, butadiene 0.2-0.3%. As a catalyst, 1,j
- Using a solution of aluminum chloride in chloroethyl at a concentration of % by weight. The reaction was measured using the following dimensions: length of tube 2
00 C0IL, the diameter of the tube is α, the length of the catalytic converter is 3α, the diameter of the catalytic converter is 1
) scrIL (the length-to-diameter ratio of the tube is J:/;
The length to diameter ratio of the catalyst inlet socket pipe is /S:/
The process is carried out in the apparatus shown in FIG. 1, with a ratio of the length of the catalytic converter to the length of the tube of 1:10.

The feedstock enters the reactor through a socket knob positioned at an angle (β) of up to 900 to the axis of the tube. Catalyst supply personnel ensure the introduction of the catalyst solution at an angle (α) of 9000 with respect to the candy feed stream. Process control is carried out chromatographically by temperature and pressure in the reaction zone and by the value of monomer conversion.

The reaction mass after reaction is treated with water (alcohol) and subjected to fractionation to separate unreacted components and light fractions of the feedstock. The polymers are analyzed for their molecular weight (freezing point depression, viscometry), molecular weight distribution (MMD) (gel chromatography).

Small polymers are also analyzed for unsaturation (by measuring their iodine number).

3. The results of the polymerization test of the fraction of 04 hydrocarbons under a pressure of two atmospheres are shown in the table below.

Table / / 23 Tei 567 g / 0.0! ; 0.0/3; θ0. ．． 33; 60
7q,'l'AX)20,/0,03 θ0,
3! 4033. /! ;'1030, Hiro 0. /3
00. ．． 3! ; 40' 9 33/.

I/O,'I O,I3 -10
0. ．． 3k! /91,7
RI Otsu0j O,'I O,/J
-1! 0. e2 'l/
90.6 1,1001, 0. lI
O,1,3-. 30 0,4t2. 72
G? ,,? 2,70070.60. knee 3
50. q2/97. b g, 300IO
lt Oo, 2-! ;0 0. '72
I7 91. Q/! ,000?
0. A O, 2-700,'f2 I2
qA,j 20,00010 0,
A O82-900,'42. ! r
9'1.3 I3,000// 0. A
O,1-900,! ;'I e 9
A, wo 9'l, 000/2 0j θ,
,? -900,! ;II 0
917.0 AI, 000/3 Zo! θ
, yo -900) da 0 tough, 2
8,000 Examples/Da~/7 In a polymerization in an apparatus similar to that described in Examples 1 to 3 above, under Example 90 conditions, but using a different introduction angle of the catalyst solution stream relative to the feed stream, the following Obtain the result (see λ below).

Table λ 1,2341! Otori g/'l JA -700, lI2
1,2 70 9/>, 0
Ko/ ,000/j OlA -700,lI2 //
1,39 720,700/A O,A
-700,17,2//i
? 0. / 20,000/7 0. A
-700, lI+2 10. 30 Coarse, Ri u&, 7θQ Example/g -2/ In an apparatus similar to that described in Examples 1-/3 under the conditions of Example g except that other angles of positioning of the feedstock inlet socket pipe were used. The polymerization carried out in gave the following results (Table 3).

Clothes 3 7K O04-! ;00. da2//30
g! ;, 9 Judah, 000/de o, b -s
o o, value /j Hiro 5 Deda, 7
ko1,000x o, b -so
o, invasion 15 60 deA, 3
21,300 pieces/0.6 -! ;0 θ, +122
0 I20 I7. ．． 3 I7. JOO Examples 22-, 26 Polymerization in an apparatus similar to that described in Examples/-/3 under the conditions of Example 10, except for other velocities of the reaction mass flow in the reactor, gave the following results: There is (table).

Table 1 Catalyst flow Reaction mass flow Feed material Molecular sweetening Speed
Temperature Speed Temperature Conversion rate 1, 2. ．． 7g! rA Kukoyu 0. A-も0 0.7
g91. ．． 3
KA, 0θ023 04 -90! OK 9
g, A glLt, 00θλhiro 0,1.
-90 3.0 5 lights
,? 90') 00yuS O06-
90!0.0 3? Beg o
io, y, oθ021, 01. -90
B; 0 0 g9,2 //2,000 cases 27~
3/ Polymerization in an apparatus similar to that described in Examples/-/3 under the conditions of Example 3 above gives the following results depending on the value of the pressure of the reaction mass stream (Table 5).

Table 5 Catalyst flow Reaction bulk flow Feed material Molecular sweetening Speed Temperature pressure Conversion rate/2 J 47 5
627 0,'l-
/j 1,0 deθ,7
11.3002g Oil
-/J2/ql,
, 3; 1,,)7029 0, II
-7! ;、? , tI9g, / 1,000.3
0 0. 'i −/3;
j, de 9wo, 0 120
3/0. II-B; ! ;, 0 9g, 9
390 Examples 32-35 Polymerizations carried out in an apparatus similar to that described in Examples/~/3 under Example 90 conditions, except that a catalyst inlet socket pipe equipped with a nozzle was used. The following results are given according to the numbers (Table 6).

Table 6 Feed material in boiling nozzle Molecular weight MMD value 32
0 LFj ko3,000
? , /33 Yu 94. ! r
2! , 000 4', review da
957. 2A, 300. 2.
De,? Evening Otsu 99. / Core 9.2θ
0 λ, / As seen from the data in Table B, the number of plates in the nozzle depends on the molecular weight distribution (MMD) of the resulting polymer.
).

Examples 36 to 39 Apparatus as described in Examples/-/3 under the conditions of Example W except for different ratios of tube length to diameter (constant ratio of catalyst inlet socket pipe length to tube length / : 20) Polymerizations in a similar apparatus gave the following results shown in Table 7 below.

Table 7 Ratio of flat tube length to feedstock molecular weight diameter Conversion rate (wt%) / λ3 da34
20: / g9,7 211,000
37! 0:/91
,3),,! ;,0003g
? &: /94,j'u! ,
30039 100: / 9g, /
Polymerizations carried out in an apparatus similar to that described in Examples/~/3, but using different ratios of catalyst inlet socket pipe length to tube length, were as follows: The following results are given depending on the ratio values (see Table 3).

Display ratio (Table 9)/
2. 7 4 (& evening 01;5
Wa53 /20,0θ0
10'l/ /:/! ; 9g, 773000 104
t2/:209k? 2,1700 Deku?
/:100? '7. / Za, Oθθ
? subject/:/! 07 &, Zal, left oo r 桔/:
Example 4'A~SO The length-to-diameter ratio of the catalyst inlet socket pipe is as described in Examples/~/3 above, except for the length of the tube, 3 m, and the diameter of the tube/reference. Polymerizations carried out in an apparatus similar to the apparatus give the following results depending on the value of this ratio (Table 7).

Table 9 Catalyst-containing iron Feed material Molecular weight Footbye Conversion rate Length to diameter ratio (weight i%) / Co 3
Doug 6 lθ: / De 3. / tal0aq −〇：
/ 9g, 7 1,110
rig sθ:l de'1.2
2. Da00 Hiroq /θO:/
De0,9. 2,7005θ
ljθ:/97. According to data from the iodometric analysis, the resulting polymer has a degree of unsaturation close to l (i.e., 7 double bonds per molecule).

[Brief explanation of drawings]

FIG. 1 is a front view of an apparatus for carrying out the method for producing an isobutylene polymer according to the present invention, FIG. 2 is a cross-sectional view taken along the line ■-■ in FIG. 1, and FIG. 3 is a cross-sectional view taken along the line ■-■. FIG. 4 is a sectional view taken along the line ■--■ in FIG. 1, and FIG. 5 is a side view of the device shown in FIG. 9. /...Pipe, Co...Catalyst inlet socket pipe, 3...
・Nozzle, q...plate, left...reaction zone, 6...opening in socket pipe, ? ...Inlet socket pipe for supplying raw materials, g...Outlet socket pipe for discharging the target product, w...recording device for temperature change of reaction mass, IO...
Recording device for pressure changes in the reaction mass, //... sampler.

Claims (1)

[Claims] 1. A reaction zone of a tubular reactor is fed with an isobutylene-containing feed stream and an acid catalyst solution stream having a temperature of 0°C to -70°C, followed by a turbulent flow along the reactor. In producing isobutylene polymers having a molecular weight of 150,000 or less in a tubular reactor by polymerizing the feed in a reactor mass stream that moves at an angle of 30° to the axis of the reactor mass flow, The catalyst solution stream is fed into the reaction zone at an angle of ˜120°, and the catalyst solution stream is fed into the reaction zone at an angle of at least 2
point and the reaction mass flow has a velocity of 0.
A method for producing an isobutylene polymer, characterized by having a speed of 3 to 15 m/sec, a temperature of 0 to 60°C, and a pressure of 1 to 5 atm. 2. The method of claim 1, wherein the catalyst solution fluid has a temperature within the range of 0<0>C to -90<0>C. 3. Add the catalyst solution to a catalyst concentration in the reaction mass of 0.01-0.
2. A process as claimed in claim 1, in which the reaction zone is introduced at a rate ensuring 5% by weight. 4. A process for producing an isobutylene polymer having a molecular weight of 300 to 1,000 as claimed in claim 1, 2 or 3, wherein the reaction mass stream has a temperature of mainly 40 to 60°C. 5. Production of an isobutylene polymer having a molecular weight of 1,100 to 20,000 according to claim 1, 2 or 3, wherein the reaction mass stream has a temperature of mainly 10 to 30°C. Law. 6. The reaction mass flow mainly has an excess of 0 to 10 °C,
A method for producing an isobutylene polymer having a molecular weight of 20,000 to 150,000 according to claim 1, 2, or 3. 7. Apparatus for carrying out the process for producing isobutylene polymers according to any of claims 1 to 6, comprising a tube (1) with separate inlets on one side for the feed material and the catalyst. In this case, the inlet for the feed material and the inlet for the catalyst are made in the form of socket pipes, the inlet socket pipe (2) for the catalyst being positioned on the end face of the tube (1) and directed inwardly, and its It has at least two openings (6) on the cylindrical surface, the axes of which are 30
forming an angle of ~90°, while the inlet socket pipe (7) for the feed material is placed on the cylindrical surface of the tube (1) close to the end face of the tube (1); the length of the tube (1) The ratio of diameter to diameter ranges from 20:1 to 100:1, and the ratio of length of socket pipe (2) to length of tube (1) for catalyst supply is 1.
:5 to 1:200, and the length-to-diameter ratio of the inlet socket pipe (2) for the catalyst is 10:1 to 15.
An apparatus for carrying out a method for producing an isobutylene polymer, characterized in that the ratio is 0:1. 8. The tube (1) additionally comprises a nozzle arranged on the catalyst supply socket pipe (2), said nozzles being positioned radially at an angle to each other and on the axis of the tube (1). According to claim 7, the tube is made in the form of 2 to 6 metal plates that are fixed to each other along their length and form the inner surface of the tube (1) and the reaction zone (5). The device described. 9. The inlet socket pipe (7) for feed material is connected to the pipe (1)
9. A device according to claim 7 or 8, positioned at an angle of 30° to 120° with respect to the axis of . 10. The feed material inlet socket pipe (7) is connected to the tube (1) such that its axis is offset with respect to the axis of said tube (1).
9. A device according to claim 7 or 8, which is oriented with respect to an end face of the.