KR20220031361A - Apparatus for manufacturing isobutene-isoprene copolymer and preparing method using the same - Google Patents

Abstract

The present invention relates to a manufacturing apparatus of isobutene-isoprene copolymer and a manufacturing method using the same. The manufacturing apparatus of isobutene-isoprene copolymer includes: a reactor; a static mixer; a first transfer line; and a second transfer line, wherein one or more of the static mixer, the first transfer line, and the second transfer line include cooling parts, respectively. According to the present invention, property change of polymer and widening of molecular weight distribution can be prevented.

Description

Apparatus for manufacturing an isobutene-isoprene copolymer and a manufacturing method using the same

The present invention relates to an apparatus for manufacturing an isobutene-isoprene copolymer and a manufacturing method using the same.

Butyl rubber (isobutene-isoprene rubber, IIR) is an isobutene-isoprene copolymer containing isobutene and about 1 to 6% isoprene, and has chemical resistance, moisture resistance, electrical insulation, etc. Because it is excellent, it is used for applications such as pressure-sensitive adhesive compositions and pressure-sensitive adhesive sheets. In addition, butyl rubber is used by crosslinking/compounding with other rubbers by performing an additional halogenation reaction on the double bond of isoprene, and has no gas permeability, so it is widely used in inner tubes and inner liners of tires.

Cationic polymerization is a representative synthesis method used for polymerization of butyl rubber, and a Lewis acid catalyst such as BF ₃ or AlCl ₃ is generally used as a catalyst. Lewis acid catalysts are vulnerable to moisture, so when they react with water, strong acids such as HCl or HF are produced, which sometimes mixes with products and causes quality degradation. In addition, due to the strong corrosiveness of the Lewis acid catalyst, it is necessary to set a high investment cost considering corrosion resistance during process design.

Cationic polymerization for the preparation of the isobutene-isoprene copolymer is mostly performed at a low temperature, and may be prepared by controlling the polymerization temperature at around -100° C. according to the molecular weight of the polymer to be prepared. In particular, for butyl rubber products of medium molecular weight or higher, polymerization must proceed by lowering the reaction temperature to a cryogenic temperature of -100°C to increase the molecular weight. There is a problem in that the investment cost increases by designing the double or triple.

Carrying out polymerization at a higher temperature than this can take advantage in terms of reduced energy consumption for cooling, but in this case, only a product with a lower molecular weight than a commercial product can be obtained, so isobutene-isoprene having a molecular weight of a commercial production level In order to prepare the copolymer, it is preferable not to increase the temperature excessively, but to perform polymerization by increasing the temperature to about -40°C.

However, in this case, as the polymerization temperature increases, the possibility that the temperature will rise to room temperature in the process of transporting the product after completion of polymerization increases. Since a polymer chain is formed, the molecular weight of the isobutene-isoprene copolymer may be lowered. As a result, there is a problem in that a polymer having a wide molecular weight distribution and exhibiting non-uniform physical properties is prepared.

Therefore, the development of an apparatus capable of producing an isobutene-isoprene copolymer having a narrow molecular weight distribution by suppressing side reactions due to temperature rise until the isobutene-isoprene copolymer is separated and obtained after the cationic polymerization is completed at a low temperature. need.

KR 1795125 B1

An object of the present invention is to provide an apparatus for producing an isobutene-isoprene copolymer capable of producing an isobutene-isoprene copolymer having a narrow molecular weight distribution, and a method for producing an isobutene-isoprene copolymer using the same.

In order to solve the above problems, the present invention is a reactor in which isobutene and isoprene is polymerized; a static mixer in which the effluent of the reactor and the polymerization terminator are mixed; a first transfer line connecting the reactor and the static mixer and provided with a polymerization terminator inlet on the line to enable line input of the polymerization terminator; and a second transfer line installed to allow the discharge to flow from the rear end of the static mixer, wherein at least one of the static mixer, the first transfer line, and the second transfer line includes cooling parts for each internal cooling An apparatus for producing a phosphorus isobutene-isoprene copolymer is provided.

In addition, the present invention comprises the steps of polymerizing and discharging isobutene and isoprene in a reactor; transferring the discharge from the reactor to the static mixer through a first transfer line, and introducing a polymerization terminator through a polymerization terminator inlet provided on the first transfer line; and mixing the effluent from the reactor and the polymerization terminator in a static mixer and discharging through a second transfer line, wherein at least one of the static mixer, the first transfer line and the second transfer line is each It provides a method for producing an isobutene-isoprene copolymer comprising cooling parts for cooling.

By using the manufacturing apparatus of the present invention, it is possible to prevent an additional side reaction from occurring after continuous polymerization of isobutene and isoprene until the isobutene-isoprene copolymer is recovered, changing the physical properties of the polymer and broadening the molecular weight distribution.

1 shows an apparatus for producing an isobutene-isoprene copolymer according to an embodiment of the present invention.
2 is a view showing (a) a cross-section of a first transfer line, (b) a cross-section of a static mixer, and (c) a cross-section of a second transfer line in the manufacturing apparatus according to an embodiment of the present invention.
3 shows a molecular weight distribution curve of the isobutene-isoprene copolymer prepared according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor appropriately defines the concept of the term in order to best describe his invention. Based on the principle that it can be done, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

1 shows an apparatus for producing an isobutene-isoprene copolymer according to an embodiment of the present invention.

Specifically, the apparatus for producing the isobutene-isoprene copolymer of the present invention includes a reactor 100 in which isobutene and isoprene are polymerized; a static mixer 200 in which the discharge of the reactor 100 and the polymerization terminator are mixed; a first transfer line 10 connecting the reactor 100 and the static mixer 200 and having a polymerization terminator inlet 11 on the line to enable the line input of the polymerization terminator; and a second transfer line 20 installed so that the discharge flows from the rear end of the static mixer 200, among the static mixer 200, the first transfer line 10, and the second transfer line 20 At least one is characterized by including cooling parts for each internal cooling.

The reactor 100 is for polymerization of isobutene and isoprene, and specifically, may be for preparing an isobutene-isoprene copolymer by polymerizing isobutene and isoprene in the presence of a hydrocarbon solvent and a catalyst. In the present invention, the structure or shape of the reactor 100 is not particularly limited, and may be a continuous reactor or a batch reactor.

A conventional polymerization reactor may be used, for example, a continuous polymerization reactor for continuously supplying a polymerization solution to a gas-liquid separation device, including a loop reactor, a continuous stirred tank reactor, etc. It is not limited thereto.

When the reactor 100 is a continuous reactor, the continuous reactor may be used to mean that two or more reactors are connected in series. When two or more reactors are connected in series, it means that the reaction solution discharged from the first reactor is supplied to the second reactor, and the reaction solution discharged from the second reactor is supplied to the next reactor. The number of the reactors may be determined according to the conversion rate of the polymerization solution containing the isobutene-isoprene copolymer discharged from the last reactor.

In the reactor 100, polymerization of isobutene and isoprene may be performed, and in this case, the polymerization may be performed at a temperature of -50 to -10°C. In terms of efficiently preparing an isobutene-isoprene copolymer having a high molecular weight and a narrow molecular weight distribution as intended in the present invention, specifically, it is to be carried out at a temperature of -50 to -20 ° C, or -45 to -30 ° C. can In addition, the polymerization reaction at the above temperature may be performed for 30 minutes to 3 hours, or 30 minutes to 1 hour.

The first transfer line 10 connects the reactor 100 and the static mixer 200 and transfers the discharge of the reactor 100 to the static mixer 200, and the first transfer line 10 has a line of a polymerization terminator. A polymerization terminator inlet 11 is provided on the line to enable the input. The polymerization terminator is introduced into the first transfer line 10 from the outside through the polymerization terminator inlet 11 , and the introduced polymerization terminator joins the first transfer line 10 and is static together with the discharge of the reactor 100 . It is transferred to the mixer 200 .

At this time, the discharge of the reactor 100 includes an isobutene-isoprene copolymer produced by polymerization of isobutene and isoprene in the reactor 100, unreacted isobutene, unreacted isoprene, a catalyst, a hydrocarbon solvent, etc. may have been

In the static mixer 200, the discharge of the transferred reactor 100 and the polymerization terminator are mixed. In the static mixer 200, the discharge of the reactor 100 and the polymerization terminator are evenly mixed to promote contact. This is to suppress the progress of the additional cationic polymerization reaction, and also to prevent the occurrence of side reactions that do not proceed in the reactor 100 so that a copolymer having a narrow molecular weight distribution and uniform physical properties is prepared.

The static mixer is a device in which heterogeneous fluids are continuously mixed while being transported and passed through the inside, and may be used to uniformly mix the fluids only by passing through the pipe without a rotating part or special power. The static mixer is formed in a cylindrical shape so that the fluid to be mixed passes through the internal structure and may be stirred at the flow rate of the fluid itself. Typical building materials for the static mixer component include, but are not limited to, stainless steel, polypropylene, Teflon, PVDF, PVC, CPVC, and polyacetal.

Mixing in the static mixer 200 is performed according to the properties of the fluid in the static mixer 200, laminar-flow mixing to mix through separation and rearrangement of each component flow, the purpose of homogenizing each flow of material Both turbulent-flow mixing, which characteristically creates and mixes a vortex, is possible. The laminar flow mixing may be performed in a spiral mixer or a mixer having a cross conduit, and for the turbulent mixing, a mixer having a cross conduit may be more suitably used.

The discharge of the static mixer 200 , that is, the mixture of the discharge of the reactor 100 and the polymerization terminator is discharged from the rear end of the static mixer 200 and flows through the second transfer line 20 .

The discharge of the static mixer 200 may be transferred through the second transfer line 20 and put into an additional post-processing line, or may be transferred to a recovery device for recovering the isobutene-isoprene copolymer.

The recovery device is a recovery device for recovering the isobutene-isoprene copolymer from the discharge of the transferred static mixer 200, for example, it may be a stripper for recovering the isobutene-isoprene copolymer by a stripping process, which may be the It may include a pressure pump for supplying the discharge of the static mixer 200 to the stripper, but is not limited thereto.

At least one of the static mixer 200, the first transfer line 10 and the second transfer line 20 includes cooling parts 40 for internal cooling, specifically the static mixer 200, Both the first transfer line 10 and the second transfer line 20 may include cooling parts 40 for internal cooling, respectively.

If the temperature is not controlled in the process of transferring the isobutene-isoprene copolymer from the discharge of the reactor 100 to obtain the isobutene-isoprene copolymer, from the moment it is discharged from the reactor 100 that is controlled at a low temperature, the discharge is caused by the ambient temperature. The temperature may be increased, and in this case, the possibility of a side reaction that does not occur at the polymerization temperature maintained in the reactor 100 is increased. Due to this, an unexpected change may occur in the physical properties of the isobutene-isoprene copolymer, and in particular, an isobutene-isoprene copolymer having a very wide molecular weight distribution or a bimodal form may be prepared.

The cooling parts 40 are for suppressing the temperature increase until the discharge of the reactor 100 reaches the recovery device.

Specifically, the first transfer line 10 for transferring the waste from the reactor 100 to the static mixer 200, the static mixer 200, and the second transfer line for transferring the waste from the static mixer 200 to the recovery device ( At least one of 20) includes cooling parts 40 for cooling them, and through this, the temperature of the first transfer line 10, the static mixer 200, and the second transfer line 20 is maintained below a certain level. This prevents the occurrence of side reactions.

The cooling parts 40 may be installed to surround the inner surface of all or a part of each in one or more of the static mixer 200 , the first transfer line 10 , and the second transfer line 20 . When the static mixer 200, the first transfer line 10, and the second transfer line 20 all include cooling parts, the cooling parts 40 are the static mixer 200 and the first transfer line 10. And the second transfer line 20 may be installed surrounding all or part of the inner surface of each. Such a structure can effectively control the temperature rise by directly contacting the static mixer 200, the first transfer line 10, and the second transfer line 20, thereby suppressing cationic polymerization of unreacted monomers. It is preferable in terms of uniformly composing the overall physical properties of the copolymer.

The cooling parts 40 may include at least one selected from the group consisting of ethane, ethylene, ethanol, propylene, and ammonia, and specifically may be ethanol, but is not limited thereto. The materials included in the cooling parts 40 are maintained in a fluid state and provided with a predetermined thickness from each inner surface in one or more of the static mixer 200, the first transfer line 10, and the second transfer line 20 has been In the present invention, materials having a lower temperature than the discharge of the reactor 100 when in a fluid state may be included in the cooling parts 40 to be used as a coolant. The material contained in the cooling parts 40 may be provided in the cooling parts 40 while flowing in a liquid state by being maintained at a temperature above the freezing point and below the boiling point, and while flowing into the liquid, the static mixer 200, the first transfer line 10 ), the temperature inside the second transfer line 20 can be maintained at a low temperature of about -10 to 50 °C.

In addition to the above-listed types, if it is a material having a temperature lower than the temperature of the discharge of the reactor 100, for example, -10 to 50° C. when in a liquid state, it is possible to include it in the cooling parts 40 and use it, at this time the cooling parts ( 40), it is required to maintain the temperature above the freezing point and below the boiling point so that it does not become solid or gaseous.

The cooling parts 40 of the static mixer 200, the first transfer line 10 and the second transfer line 20 are each independently 0.125 to 1 inch, specifically 0.125 inch or more, 0.25 inch from the inner surface. It may have a thickness of 1 inch or less, 0.7 inch or less, 0.5 inch or less, or 0.4 inch or less. When the thickness of the cooling parts 40 is less than 0.125 inches, the effect of preventing the internal temperature rise of each of the static mixer 200, the first transfer line 10 and the second transfer line 20 may not be sufficiently implemented, When the thickness of the cooling parts 40 is more than 1 inch, the effect of maintaining a low temperature compared to the thickness of the cooling parts 40 does not increase, so a problem in economic efficiency may appear.

The static mixer 200, the first transfer line 10, and the cooling parts 40 of the second transfer line 20 are inside the static mixer 200, the first transfer line 10, the second transfer line ( 20) in order to prevent each internal temperature rise.

The cooling parts 40 of the static mixer 200 are for preventing the temperature rise inside the static mixer 200, and the temperature when the discharge of the reactor 100 and the polymerization terminator are mixed while flowing through the static mixer 200 to suppress the rise of By providing the cooling parts 40, the internal temperature of the static mixer 200 can be maintained at -50 to -10°C, and in this temperature range, the occurrence of side reactions is suppressed and finally isobutene-isoprene with uniform physical properties to obtain a copolymer. In addition, since the temperature inside the static mixer 200 is kept low, the discharge of the reactor 100 and the polymerization terminator can be more evenly mixed, so that the cationic polymerization of isobutene and isoprene can be reliably terminated.

The cooling parts 40 of the first transfer line 10 are for preventing the temperature rise inside the first transfer line 10 , and the discharge of the reactor 100 and the polymerization terminator injected into the polymerization terminator inlet 11 . , in order to suppress the temperature increase while the mixture is transferred to the static mixer 200 while flowing to the first transfer line 10 . By providing the cooling parts 40, the temperature inside the first transfer line 10 can be maintained at -50 to -10°C, and in this temperature range, the occurrence of side reactions is suppressed and finally isobutene with uniform physical properties. - makes it possible to obtain an isoprene copolymer.

The cooling parts 40 of the second transfer line 20 are to prevent the temperature rise inside the second transfer line 20, and to suppress the temperature rise while the discharge from the rear end of the static mixer 200 flows. am. In the static mixer 200, the discharge of the reactor 100 and the polymerization terminator are mixed, but not all cationic polymerization is completely terminated, and the possibility of side reactions still remains, so the temperature until finally recovering and obtaining the isobutene-isoprene copolymer By preventing the rise, the occurrence of side reactions is suppressed. By providing the cooling parts 40, the temperature inside the second transfer line 20 can be maintained at -50 to -10°C, and in this temperature range, the occurrence of side reactions is suppressed and finally isobutene with uniform physical properties. - makes it possible to obtain an isoprene copolymer.

The method for preparing the isobutene-isoprene copolymer of the present invention comprises the steps of polymerizing and discharging isobutene and isoprene in a reactor; transferring the discharge from the reactor to the static mixer through a first transfer line, and introducing a polymerization terminator through a polymerization terminator inlet provided on the first transfer line; and mixing the effluent from the reactor and the polymerization terminator in a static mixer and discharging through a second transfer line, wherein at least one of the static mixer, the first transfer line and the second transfer line is each It is characterized in that it includes cooling parts for cooling.

Specifically, all of the static mixer, the first transfer line, and the second transfer line may include cooling parts 40 for internal cooling.

The method for producing the isobutene-isoprene copolymer may be carried out using the above-described apparatus for producing the isobutene-isoprene copolymer of the present invention.

In the reactor, polymerization of isobutene and isoprene can be carried out, and the polymerization reaction can be carried out at a temperature of -50 to -10 °C, and isobutene having a high molecular weight and a narrow molecular weight distribution as intended in the present invention- In terms of efficiently preparing the isoprene copolymer, it may be specifically carried out at a temperature of -50 to -20°C, or -45 to -30°C. In addition, the polymerization reaction at the above temperature may be performed for 30 minutes to 3 hours, or 30 minutes to 1 hour.

In addition, the temperature of the effluent of the reactor flowing through the first transfer line and the effluent of the static mixer flowing through the second transfer line may be maintained at -50 to -10°C.

The polymerization of isobutene and isoprene in the reactor may be carried out by solvent polymerization, and specifically, it may be carried out including a halogenated hydrocarbon solvent and a non-polar hydrocarbon solvent.

The halogenated hydrocarbon solvent may be at least one selected from the group consisting of chloromethane, dichloromethane, trichloromethane, 1-chlorobutane and chlorobenzene, and the non-polar hydrocarbon solvent may be an aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent. there is. For example, the aliphatic hydrocarbon solvent may be at least one selected from the group consisting of butane, pentane, neo pentane, hexane, cyclohexane, methyl cyclohexane, heptane and octane, and the aromatic hydrocarbon solvent is benzene, toluene, xylene , may be at least one selected from the group consisting of ethylbenzene

In addition, as long as the polymerization is a catalyst capable of cationic polymerization of isobutene and isoprene to form an isobutene-isoprene copolymer, it can be used without limitation in its structure or type, and a cocatalyst capable of activating the catalyst is also used in various ways. possible.

Specifically, the catalyst composition used for polymerization of isobutene and isoprene in a reactor in the manufacturing apparatus and manufacturing method of the present invention may include a catalyst represented by the following Chemical Formula 1 and a promoter represented by Chemical Formula 2 below.

[Formula 1]

In Formula 1,

R is an alkyl group having 2 to 12 carbon atoms,

R ₁ to R ₄ are each independently a halogen group,

o, p, q and r are each independently an integer of 1 to 5,

[Formula 2]

In Formula 2,

R _a is a hydrocarbon group having 1 to 20 carbon atoms,

Z is a halogen group,

m is an integer from 0 to 3.

In Formula 1, may be an alkyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 6 carbon atoms, an alkyl group having 2 to 4 carbon atoms, or an ethyl group, and R ₁ to R ₄ are each independently a halogen group, specifically, a fluorine group and o, p, q and r may each independently be an integer of 1 to 5, specifically, an integer of 4 or 5. Most preferably, while R ₁ to R ₄ are a fluorine group, o, p, q and r may be 5.

는 구체적으로 테트라키스(펜타플루오로페닐)보레이트일 수 있다.In addition, the organic borate contained in the compound represented by Formula 1

may be specifically tetrakis(pentafluorophenyl)borate.

In Chemical Formula 2, R _a may each independently be an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, 1 to carbon atoms It may be an alkyl group of 6, an alkyl group of 1 to 3 carbon atoms, or an ethyl group.

Z may be preferably a chloride group or a bromide group, preferably a chloride group, and m may be an integer of 2 or 3, preferably 3.

The promoter represented by Formula 2 is trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum , trialkyl aluminum, such as trihexyl aluminum, tricyclohexyl aluminum, trioctyla aluminum, and tri-2-ethylhexyl aluminum; dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, and dimethyl aluminum bromide; alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, and ethyl aluminum dibromide; aluminum trichloride; Or a combination thereof may be used, but is not limited thereto.

The combination of the catalyst and the cocatalyst may be suitably used to prepare an isobutene-isoprene copolymer by polymerizing isobutene and isoprene at a polymerization temperature of -50 to -10°C as described above.

According to an embodiment of the present invention, a high weight average molecular weight and narrow molecular weight distribution using a catalyst composition including a catalyst represented by Formula 1 and a cocatalyst represented by Formula 2 in a reactor using the production apparatus of the present invention After preparing an isobutene-isoprene copolymer having It is possible to obtain a copolymer having desirable physical properties without

Example

Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto.

Example 1

While maintaining the continuous reactor connected to the cooling device at -40 to 30°C, isobutene and isoprene were continuously injected together with the solvent, and a mixture of catalyst and cocatalyst was also continuously injected. While stirring the injected raw material, the average residence time was set to 30 to 60 minutes.

After completion of the reaction, the polymerization product discharged from the continuous reactor was transferred to the static mixer through the first transfer line, and at this time, 200 equivalents of methanol as a polymerization stopper was injected based on 1 equivalent of the catalyst during the transfer.

The static mixer has a bar grid structure crossed at 45 degrees to the pipe axis, and the polymerization product and methanol were mixed using a static mixer for laminar flow, and then transferred to a recovery device (pump) through the second transfer line and passed After washing, the catalyst and the cocatalyst were removed from the resulting solution through a filter to obtain an isobutene-isoprene copolymer.

The first transfer line, the static mixer, and the second transfer line had a thickness of 0.25 inches and were equipped with cooling parts made of ethanol.

Example 2

While maintaining the continuous reactor connected to the cooling device at -40 to 30°C, isobutene and isoprene were continuously injected together with the solvent, and a mixture of catalyst and cocatalyst was also continuously injected. While stirring the injected raw material, the average residence time was set to 30 to 60 minutes.

After completion of the reaction, the polymerization product discharged from the continuous reactor was transferred to the static mixer through the first transfer line, and at this time, 200 equivalents of methanol as a polymerization stopper was injected based on 1 equivalent of the catalyst during the transfer.

As a static mixer, a corrugated plate at 45 degrees or 30 degrees to the pipe axis has a structure consisting of adjacent mixing elements at 90 degrees, and the polymerization product and methanol were mixed using a static mixer for turbulent flow, and then recovered through the second transfer line. After passing through the device (pump), the catalyst and co-catalyst were removed from the resulting solution through a filter to obtain an isobutene-isoprene copolymer.

The first transfer line, the static mixer, and the second transfer line had a thickness of 0.25 inches and were equipped with cooling parts made of ethanol.

Comparative Example 1

While maintaining the continuous reactor connected to the cooling device at -40 to 30°C, isobutene and isoprene were continuously injected together with the solvent, and a mixture of catalyst and cocatalyst was also continuously injected. While stirring the injected raw material, the average residence time was set to 30 to 60 minutes.

After completion of the reaction, the catalyst and co-catalyst were removed from the solution obtained after being transferred to a recovery device (pump) and passed through a filter to obtain an isobutene-isoprene copolymer.

Comparative Example 2

While maintaining the continuous reactor connected to the cooling device at -40 to 30°C, isobutene and isoprene were continuously injected together with the solvent, and a mixture of catalyst and cocatalyst was also continuously injected. While stirring the injected raw material, the average residence time was set to 30 to 60 minutes.

After completion of the reaction, the polymerization product discharged from the continuous reactor was transferred to a recovery device (pump) and passed, and the resulting solution was transferred to a filter. did The catalyst and co-catalyst were removed through a filter to obtain an isobutene-isoprene copolymer.

Comparative Example 3

While maintaining the continuous reactor connected to the cooling device at -40 to 30°C, isobutene and isoprene were continuously injected together with the solvent, and a mixture of catalyst and cocatalyst was also continuously injected. While stirring the injected raw material, the average residence time was set to 30 to 60 minutes.

After completion of the reaction, the polymerization product discharged from the continuous reactor was transferred to a recovery device (pump), and during the transfer, 150 equivalents of methanol was injected as a polymerization terminator based on 1 equivalent of the catalyst. The catalyst and co-catalyst were removed through a filter to obtain an isobutene-isoprene copolymer.

Comparative Example 4

An isobutene-isoprene copolymer was obtained in the same manner as in Comparative Example 3, except that 200 equivalents of methanol was injected based on 1 equivalent of the catalyst.

Comparative Example 5

An isobutene-isoprene copolymer was obtained in the same manner as in Comparative Example 3, except that 300 equivalents of methanol was injected based on 1 equivalent of the catalyst.

Comparative Example 6

An isobutene-isoprene copolymer was obtained in the same manner as in Comparative Example 3, except that 200 equivalents of water was injected based on 1 equivalent of catalyst instead of methanol.

Comparative Example 7

While maintaining the continuous reactor connected to the cooling device at -40 to 30°C, isobutene and isoprene were continuously injected together with the solvent, and a mixture of catalyst and cocatalyst was also continuously injected. While stirring the injected raw material, the average residence time was set to 30 to 60 minutes.

After completion of the reaction, the polymerization product discharged from the continuous reactor was transferred to the static mixer through the first transfer line, and at this time, 200 equivalents of methanol as a polymerization stopper was injected based on 1 equivalent of the catalyst during the transfer.

The static mixer has a bar grid structure crossed at 45 degrees to the pipe axis, and the polymerization product and methanol were mixed using a static mixer for laminar flow, and then transferred to a recovery device (pump) through the second transfer line and passed After washing, the catalyst and the cocatalyst were removed from the resulting solution through a filter to obtain an isobutene-isoprene copolymer.

Comparative Example 8

While maintaining the continuous reactor connected to the cooling device at -40 to 30°C, isobutene and isoprene were continuously injected together with the solvent, and a mixture of catalyst and cocatalyst was also continuously injected. While stirring the injected raw material, the average residence time was set to 30 to 60 minutes.

After completion of the reaction, the polymerization product discharged from the continuous reactor was transferred to the static mixer through the first transfer line, and at this time, 200 equivalents of methanol as a polymerization stopper was injected based on 1 equivalent of the catalyst during the transfer.

As a static mixer, a corrugated plate at 45 degrees or 30 degrees to the pipe axis has a structure consisting of adjacent mixing elements at 90 degrees, and the polymerization product and methanol were mixed using a static mixer for turbulent flow, and then recovered through the second transfer line. After passing through the device (pump), the catalyst and co-catalyst were removed from the resulting solution through a filter to obtain an isobutene-isoprene copolymer.

Where to put the polymerization stopper Polymerization inhibitor type Polymerization inhibitor input amount (based on 1 equivalent of catalyst) static mixer cooling parts Example 1 Between Reactor-Static Mixer methanol 200 equivalents Laminar flow Ethanol, 0.25 inch Example 2 Between Reactor-Static Mixer methanol 200 equivalents Turbulent flow Ethanol, 0.25 inch Comparative Example 1 - - - - - Comparative Example 2 rear end of recovery device methanol 200 equivalents - - Comparative Example 3 Between reactor and recovery device methanol 150 equivalents - - Comparative Example 4 Between reactor and recovery device methanol 200 equivalents - - Comparative Example 5 Between reactor and recovery device methanol 300 equivalents - - Comparative Example 6 Between reactor and recovery device water 200 equivalents - - Comparative Example 7 Between Reactor-Static Mixer methanol 200 equivalents Laminar flow - Comparative Example 8 Between Reactor-Static Mixer methanol 200 equivalents Turbulent flow -

Experimental Example 1

(1) Yield (%)

- Yield (%) = (Isobutene-isoprene copolymer weight (g)) / (isobutene weight (g)) + (isoprene weight (g))

(2) number average molecular weight, weight average molecular weight, molecular weight distribution

The isobutene-isoprene copolymer was measured under the following gel permeation chromatography (GPC) analysis conditions to measure the number average molecular weight (Mn) and the weight average molecular weight (Mw), and (weight average molecular weight) / (number average molecular weight) as a value The molecular weight distribution was calculated.

- Column: PL MiniMixed B × 2

- Solvent: THF

- Flow rate: 0.3 ml/min

- Sample concentration: 2.0 mg/ml

- Injection volume: 10 μL

- Column temperature: 40℃

- Detector: Agilent RI detector

- Standard: Polystyrene (corrected by cubic function)

- Data processing: ChemStation

(3) isoprene content (mol%)

¹ H NMR was measured using 500 MHz NMR (Agilent Co.) (Sample concentration: 0.5 wt%, solvent: CDCl ₃ ). The presence of isoprene in the copolymer was confirmed in ¹ H NMR spectrum, and the isoprene content was calculated by the following formula.

-isoprene content (mol%) = (moles of isoprene in the copolymer)/(moles of isobutene in the copolymer)+(moles of isoprene in the copolymer)

transference number(%) Mn Mw MWD IP content (mol%) Example 1 65 242,000 562,000 2.3 2.0 Example 2 61 208,000 520,000 2.5 1.9 Comparative Example 1 64 46,000 300,000 6.5 2.0 Comparative Example 2 60 66,000 422,000 6.4 1.9 Comparative Example 3 51 94,000 414,000 4.4 1.8 Comparative Example 4 50 147,000 441,000 3.0 1.8 Comparative Example 5 54 118,000 426,000 3.6 1.8 Comparative Example 6 52 123,000 392,000 3.2 1.8 Comparative Example 7 49 180,000 467,000 2.6 1.9 Comparative Example 8 50 163,000 472,000 2.9 1.8

As shown in Table 2, in the case of Examples 1 and 2, in which the isobutene-isoprene copolymer was prepared using the manufacturing apparatus of the present invention, the isobutene-isoprene copolymer having a narrow molecular weight distribution and high molecular weight was prepared in excellent yield. On the other hand, Comparative Example 1, in which no polymerization inhibitor was added, had a very low molecular weight and a broad molecular weight distribution, and Comparative Example using a device in which a polymerization inhibitor was added but not equipped with a static mixer In 2 to 6, an isobutene-isoprene copolymer having a wide molecular weight distribution and a small molecular weight was prepared compared to Examples in both cases when the injection position of the polymerization inhibitor was at the front or rear end of the recovery device.

In addition, in the case of Comparative Examples 7 and 8, it seems that it was difficult to control the temperature rise by using a device without cooling parts, respectively, and the molecular weight distribution of the isobutene-isoprene copolymer when compared with Examples 1 and 2, respectively It can be seen that the width is wide and the molecular weight is small.

Through these results, the production apparatus of the present invention injects a polymerization terminator and mixes it in a static mixer, and since cooling parts are provided in the transfer line and the static mixer, a high molecular weight isobutene-isoprene copolymer having a narrow molecular weight distribution It was confirmed that it can be prepared.

100: reactor
200: static mixer
10: first transfer line
11: polymerization terminator inlet
20: second transfer line
40: cooling parts

Claims (11)

a reactor in which isobutene and isoprene are polymerized;
a static mixer in which the effluent of the reactor and the polymerization terminator are mixed;
a first transfer line connecting the reactor and the static mixer and provided with a polymerization terminator inlet on the line to enable line input of the polymerization terminator; and
Includes; a second transfer line installed to flow the discharge from the rear end of the static mixer;
At least one of the static mixer, the first transfer line, and the second transfer line includes cooling parts for each internal cooling, isobutene-isoprene copolymer manufacturing apparatus.
The method according to claim 1,
The static mixer, the first transfer line and the second transfer line is an apparatus for producing an isobutene-isoprene copolymer comprising cooling parts for internal cooling, respectively.
The method according to claim 1,
The cooling parts are, in one or more of the static mixer, the first transfer line and the second transfer line, the isobutene-isoprene copolymer manufacturing apparatus that surrounds the inner surface of all or a part of each.
The method according to claim 1,
The cooling parts are, in at least one of the static mixer, the first transfer line and the second transfer line, each having a thickness of 0.125 to 1 inch from the inner surface of the isobutene-isoprene copolymer manufacturing apparatus.
The method according to claim 1,
The cooling parts include at least one selected from the group consisting of ethane, ethylene, ethanol, propylene and ammonia.
The method according to claim 1,
The internal temperature of the static mixer, the first transfer line and the second transfer line is -50 to -10 ℃ isobutene-isoprene copolymer manufacturing apparatus.
polymerizing and discharging isobutene and isoprene in a reactor;
transferring the discharge from the reactor to a static mixer through a first transfer line, and introducing a polymerization terminator through a polymerization terminator inlet provided on the first transfer line; and
mixing the effluent of the reactor and the polymerization terminator in a static mixer and discharging through a second transfer line;
At least one of the static mixer, the first transfer line, and the second transfer line includes cooling parts for internal cooling, respectively.
8. The method of claim 7,
The static mixer, the first transfer line and the second transfer line is an apparatus for producing an isobutene-isoprene copolymer comprising cooling parts for internal cooling, respectively.
8. The method of claim 7,
The polymerization of isobutene and isoprene is a method for producing an isobutene-isoprene copolymer is carried out at a temperature of -50 to -10 ℃.
8. The method of claim 7,
The discharge temperature of the reactor transferred to the first transfer line is -50 to -10 ℃ method for producing an isobutene-isoprene copolymer.
8. The method of claim 7,
The discharge temperature of the static mixer flowing through the second transfer line is -50 to -10 ℃ method for producing an isobutene-isoprene copolymer.

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