JP5365913B2 - Continuous production method of living cationic polymer - Google Patents

Description

  The present invention relates to a continuous production method of a living cationic polymerization reaction.

  Living polymerization consists of an initiation reaction and a growth reaction, and refers to a chain polymerization that does not involve side reactions such as a termination reaction or a chain transfer reaction. In the narrow sense, the polymer growth end always maintains activity and the molecular chain grows. In general, this also includes quasi-living polymerization in which molecular chains grow while the polymerization growth terminal is deactivated and the activated one is in an equilibrium state. In such living polymerization, if the polymerization reaction starts simultaneously, a polymer having a low degree of dispersion can be obtained, and a specific functional group can be introduced into the active terminal of the polymer, or two or more monomers can be used. Thus, a copolymer can be synthesized.

  As living polymerization carried out industrially, for example, living cationic polymerization of isobutylene described in Patent Literature 1 and Patent Literature 2 can be mentioned. As described above, there are many reports on the operation mode of the living polymerization reaction that are carried out batchwise by using a stirred tank reactor and charging reaction raw materials into the polymerization tank.

  In batch polymerization, in either method, the reactor size is increased in order to increase productivity, and the heat removal area is increased by the internal coil cooling method, reflux condenser method, etc. Semi-batch polymerization methods have been used. However, in this case, the equipment cost increases due to the increase in size and complexity of the heat removal equipment. When trying to suppress the equipment cost, it becomes difficult to control the internal temperature, side reactions increase, and it becomes difficult to obtain a polymer having a low degree of dispersion, which is a characteristic of living polymerization.

  On the other hand, a continuous polymerization system in which raw materials are continuously supplied to a reactor has been attempted with the aim of improving productivity. For example, Patent Document 3 attempts a method of conducting living cationic polymerization by continuously supplying a polymerization initiator, a Lewis acid catalyst, and isobutylene to a single stirred tank reactor.

  Patent Document 4 proposes a method of introducing a vinyl group at the end of a polymer in a tubular reactor after continuous living cationic polymerization of isobutylene using a shell-and-tube heat exchanger. . In Patent Documents 5, 6, and 7, the living cationic polymerization of isobutylene is continuously supplied to the flow-type stirred tank reactor to start the reaction, and then continuously supplied to the flow-tube reactor to perform the living polymerization. Progressing. Patent Document 8 attempts to perform continuous living anionic polymerization in a tubular reactor.

  However, some problems still remain when performing continuous polymerization. That is, as a result of continuous polymerization in one stirred tank reactor, in Patent Document 3, the obtained polymer has a molecular weight dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.4 to 1. 8 and the degree of dispersion is higher than in batch polymerization. In such a tendency, when the continuous reaction is carried out in one stirring tank, the residence time of the reaction solution has a wide distribution (that is, the residence time in the tank differs for each polymer molecule). This is considered to be due to the fact that the lengths of molecular chains grown by living polymerization are difficult to align.

  In continuous polymerization, side reactions may be a problem, and the degree of dispersion is not sufficiently reduced only by narrowing the residence time distribution. In Patent Document 4, since the tubular reactor is used, the dispersion degree of the obtained polymer is as large as 3.1 even though the residence time of the reaction solution is considered to be uniform. In Patent Documents 5, 6, and 7, the molecular weight dispersity is improved by 1.2 to 1.3 by passing through a tubular reactor after passing one stirring tank, but a stirring tank is used. As a result, concerns remain about the residence time distribution. Furthermore, big problems remain from the viewpoints of complicated mixing conditions in the tank, side reaction control, and heat removal efficiency when scaled up. In Patent Document 8, the degree of dispersion of the obtained acrylic polymer is 1.3 to 1.8, which is relatively high.

  When these tubular reactors are used, the living polymerization initiation reaction may be caused by insufficient mixing immediately after the feed of the raw materials to the reactor or insufficient heat removal from the polymerization reaction heat. It is presumed that the side reaction was accompanied by an inappropriate reaction.

  Among various polymerization reactions, living cationic polymerization controls the initiation reaction by applying special measures to the catalyst and additives, or polymerizes because the polymerization activity decreases or side reactions occur at relatively low temperatures. It seems that it was relatively difficult to apply the continuous method because it was important to remove the heat of reaction.

  As described above, when living polymerization is carried out continuously, there is a problem that the degree of dispersion of the resulting polymer increases due to the spread of residence time distribution and side reactions. When the degree of dispersion increases, the viscosity of the polymer increases, which is a serious problem depending on the use of the polymer, and the development of the use is hindered. Among these, the side reaction problem is not only that the degree of dispersion of the polymer increases, but also the growth terminal of the polymer is not controlled, so the introduction of functional groups at the polymer terminal and the synthesis of the block body are as originally designed. There is a problem of not becoming. These are important problems specific to continuous operation.

JP 7-292038 A JP-A-8-53514 U.S. Pat. No. 4,568,732 Japanese Patent Laid-Open No. Hei 6-298443 JP 2001-55407 A JP 2001-55408 A JP 2001-55415 A Japanese Patent Laid-Open No. 11-286520

  In view of the above-mentioned present situation, an object of the present invention is to provide a production method capable of continuously obtaining a polymer having a low molecular weight dispersity. Moreover, the objective of this invention is also providing the continuous manufacturing method of a living cationic polymer which can be implemented with the compact installation which can control the internal temperature of a reactor effectively. Furthermore, an object of the present invention is to provide a continuous production method in which a living cationic polymer can be obtained as originally designed by introduction of a functional group at a terminal or synthesis of a block body.

In the present invention, a solution (A) containing a polymerization initiator, a polymerizable monomer, and a polymerization solvent and a solution (B) containing a catalyst and a polymerization solvent are separately and continuously supplied to a static mixer. after mixing both solutions Te, relates to a process for continuous production living cationic polymer, characterized in that the polymerization is carried out by supplying to the tubular reactor.

  Preferably, the present invention relates to a continuous production method of a living cationic polymer, wherein the solution (A) contains an electron donor.

  Preferably, the present invention relates to a continuous production method of a living cationic polymer, wherein an electron donor is present in a molar ratio of 1 to 5 times with respect to a polymerization initiator in a tubular reactor.

  Preferably, the present invention relates to a continuous production method of a living cationic polymer, characterized in that a catalyst is present in a molar ratio of 1 to 50 times with respect to a polymerization initiator in a tubular reactor.

  Preferably, the present invention relates to a continuous production method of a living cationic polymer, characterized in that the average flow velocity in the tube of the solution passing through the tubular reactor is 0.01 to 1 m / s.

  Preferably, the present invention relates to a continuous production method of a living cationic polymer, wherein the ratio L / D between the length L of the tubular reactor and the tube diameter D is 10 or more.

  Preferably, the present invention relates to a continuous production method of a living cationic polymer, wherein the polymerizable monomer is a cationic polymerizable monomer component containing at least isobutylene, and the catalyst is a Lewis acid catalyst.

  Preferably, the polymerization initiator is (1-chloro-1-methylethyl) benzene, 1,4-bis (1-chloro-1-methylethyl) benzene, and 1,3,5-tris (1-chloro- The present invention relates to a continuous production method of a living cationic polymer, characterized in that it is at least one compound selected from the group consisting of 1-methylethyl) benzene.

  Preferably, the polymerization solvent is a mixed solvent in which a primary and / or secondary monohalogenated hydrocarbon having 3 to 8 carbon atoms and an aliphatic and / or aromatic hydrocarbon are combined. The present invention relates to a continuous production method of a living cationic polymer.

  Preferably, the present invention relates to a continuous production method of a living cationic polymer, wherein the polymerization solvent is a mixed solvent of n-butyl chloride and n-hexane.

  Preferably, the present invention relates to a continuous production method of a living cationic polymer, wherein the polymerization temperature is −80 to −10 ° C.

  The continuous production method according to the present invention makes it possible to keep the residence time constant (narrow residence time distribution) and to control side reactions. It is effective in that it can maintain a small and constant value from the subsequent growth process.

It is the schematic which shows the flowchart of an example of the living cationic polymer continuous manufacturing apparatus used for this invention.

(Reactor type)
A static mixer is a tubular reactor incorporating one or more static mixers composed of a large number of mixing elements. For example, a known static mixer such as a Sulzer type, Kenix type, Toray type, Noritake company type, etc. In particular, those having 4 or more mixing elements are preferable, and those having 6 to 30 mixing elements are more preferable, but not limited thereto.

  The tubular reactor is not particularly limited as long as it is a tubular reactor capable of simultaneously supplying and discharging liquid. For example, a straight tube type, a serpentine tube type, a double tube type, a shell and tube type, and the like can be mentioned, but not limited thereto.

  The length and tube diameter of the tubular reactor are preferably designed in consideration of the set molecular weight and flow rate. In the continuous production method of the present invention, the ratio L / D between the length L [m] of the tubular reactor and the tube diameter D [mm] is preferably 10 or more, and more preferably 100 or more.

  In the continuous production method of the present invention, a reaction solution in which a polymerization reaction has sufficiently progressed can be continuously taken out from a tubular reactor. Alternatively, the living polymerization reaction can be continued by continuously mixing the polymerizable monomer at the outlet or in the middle of the tubular reactor. Alternatively, by continuously mixing another polymerizable monomer at the outlet or in the middle of the tubular reactor, the copolymer synthesis reaction can be continued. Furthermore, the synthesis reaction of the block copolymer can be continued by continuously mixing another polymerizable monomer at the outlet or in the middle of the tubular reactor.

  In order to obtain the block copolymer, for example, continuous living polymerization is performed as described above, and the second polymerizable monomer component different from the first polymerizable monomer component is provided at the outlet or in the middle of the tubular reactor. Can be continuously fed from another route, mixed through two parts by passing through a static mixer, and then fed to a tubular reactor to grow a block copolymer, thereby allowing living polymerization to occur. This is preferable, but not limited to this. The first tubular reactor and the second static mixer may be directly connected or indirectly connected through one or more reactors.

  After the reaction liquid taken out is deactivated with water or alcohols, for example, the two phases are separated, the organic phase is washed with water as necessary, and the organic solvent is distilled off to obtain a polymer. it can.

(Polymerizable monomer component)
The polymerizable monomer component used in the present invention is not particularly limited as long as a polymer can be obtained by using a polymerization initiator and a catalyst. The second polymerizable monomer component used for obtaining the block copolymer has a compound and / or composition different from that of the first polymerizable monomer component, and the first polymerizable monomer What is necessary is just to be able to couple | bond with the active terminal of the polymer comprised from a body component by copolymerization. As the first polymerizable monomer component and the second polymerizable monomer component, polymerizable monomers that can be applied in various polymerization systems described below can be used without any particular limitation. Various polymerizable monomers may be used alone or in combination of two or more.

(Molecular weight of polymer)
The number average molecular weight of the polymer produced by the method of the present invention is not particularly limited, but is usually 500 to 300,000, more preferably 3000 to 150,000.

(Applicable reaction systems)
The living polymerization reaction applied in the present invention is not particularly limited, and examples thereof include living anion polymerization, living cation polymerization, living radical polymerization, living coordination polymerization, and living ring-opening polymerization. The production method of the present invention is particularly effective for living cationic polymerization. Details of the living cationic polymerization will be described below.

(Living cationic polymerization)
As living cationic polymerization, for example, synthesis described in JP Kennedy et al. (Carbocationic Polymerization, John Wiley & Sons, 1982) and K. Matyjaszewski et al. (Cationic Polymerizations, Marcel Dekker, 1996) can be applied.

(Raw material supply method)
The present invention relates to a continuous production method of a living cationic polymer, a solution (A) containing a polymerization initiator, a polymerizable monomer, and a polymerization solvent, and a solution (B) containing a catalyst and a polymerization solvent. Are continuously mixed by a static mixer and supplied to a tubular reactor for polymerization.

  A raw material liquid containing a polymerizable monomer component and a raw material liquid containing a catalyst are separately charged into a pressure stirrer, and are continuously supplied to a static mixer to mix both raw material liquids to start living cationic polymerization. It is a feature. A raw material liquid can also be supplied by mixing a polymerization initiator in advance in the cationic polymerizable monomer. Thereby, the residence time can be made constant (the residence time distribution is narrowed), and the side reaction can be controlled. Therefore, the molecular weight dispersity of the resulting living polymer is small (for example, 1.1 to 1.2) from the growth process after the start of polymerization, and can maintain a constant value.

  As a liquid feeding method, nitrogen can be filled in a pressure-resistant stirrer, and pressure feeding can be performed. However, the liquid feeding method is not particularly limited, and for example, supply by a pump is also conceivable as another liquid feeding method, but this is not restrictive.

  In consideration of the tube diameter, the tube length, the pressure, the residence time in the tube, the polymer molecular weight, the polymer viscosity and the like, the liquid feeding speed is preferably in the range of 0.01 to 1 m / s as the average flow velocity in the tube, 0.02 to 0 A range of 0.5 m / s is more preferable.

  When the liquid feeding speed is 0.01 m / s or less, the average flow velocity in the tube is slow, so that the residence time distribution becomes wide and a polymer as designed cannot be obtained. If the average flow velocity in the tube is 1 m / s or more, the residence time distribution becomes narrow because of the high average flow velocity in the tube. Since many monomers remain, a polymer as designed cannot be obtained. Alternatively, by using a sufficiently long tube reactor, the remaining of unreacted monomer is avoided, but the tube length cannot be practically used. As described above, the liquid feeding speed needs to be set within a practically applicable range in consideration of these points, and also the set molecular weight, tube diameter, tube length, and the like.

(Polymerization initiator used)
As an efficient method for initiating living cationic polymerization, an inifer method has been developed in which a compound such as a compound having a chlorine atom bonded to a tertiary carbon or a chlorine compound having an aromatic ring at the α-position is used as a polymerization initiator. This method can be applied to the present invention. The polymerization initiator used in the inifer method only needs to exhibit its function, and typical examples thereof include those having the following structure.
(X-CR ¹ R ² ) _n R ³
(In the formula, X represents a halogen atom. R ¹ and R ² are the same or different and represent a monovalent hydrocarbon group having 1 to 20 carbon atoms. R ³ is an n-valent having 1 to 20 carbon atoms. And n is an integer of 1 to 4.)
Typical polymerization initiators include (1-chloro-1-methylethyl) benzene, 1,4-bis (1-chloro-1-methylethyl) benzene (hereinafter p-DCC), and 1,3,5. -Tris (1-chloro-1-methylethyl) benzene (hereinafter referred to as TCC). These can be used alone or as a mixture. Thus, an initiator containing an aromatic ring is more preferable. A bifunctional initiator such as p-DCC can be selected when a bifunctional polymer is required. In addition, monofunctional, trifunctional and polyfunctional initiators such as TCC can be used as necessary. The molecular weight of the polymer can be freely set according to the charging ratio between the polymerization initiator and the monomer.

(Catalyst used)
The catalyst used for the living cationic polymerization is a Lewis acid catalyst, and specific examples thereof include TiCl ₄ , AlCl ₄ , BCl ₃ , ZnCl ₂ , SnCl ₄ , ethylaluminum chloride, SnBr _{4 and the} like. The amount of Lewis acid catalyst used is preferably 1 to 50 times the molar amount of the polymerization initiator. That is, in the present invention, the catalyst is preferably present in a molar ratio of 1 to 50 times the polymerization initiator in the tubular reactor of the solution mixed by the static mixer.

(Electron donor)
When using the above-described inifer method, it is effective to use an electron donor in order to obtain a good polymer by suppressing side reactions such as chain transfer reaction and proton initiation reaction (Japanese Patent Laid-Open No. 2-245004). No. 1, JP-A-1-318014, JP-A-3-174403).

The electron donor is not particularly limited, and examples thereof include pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom. Specifically, pyridine, 2-methylpyridine (abbreviated as picoline or α-picoline), trimethylamine, dimethylacetamide (abbreviated as DMAc), dimethyl sulfoxide (DMSO), ethyl acetate (EtOAc), Ti (OiPr) _{4 and the} like. Preferably used.

  The electron donor is preferably present in the reaction system in a molar ratio of 1 to 10 times that of the polymerization initiator. If the amount of the electron donor is too small, side reactions tend to increase, and the degree of dispersion increases due to the proton initiation reaction and chain transfer reaction. Conversely, when there are too many electron donors, the polymerization reaction rate is remarkably suppressed, and the cationic polymerization reaction takes a long time, and the productivity is lowered. Therefore, the more preferable amount of the electron donor is in the range of 1 to 5 times the molar ratio with respect to the polymerization initiator. That is, in the present invention, in the tubular reactor of the solution mixed by the static mixer, it is preferable that the electron donor is present in a molar ratio of 1 to 5 times with respect to the polymerization initiator.

  In the present invention, a solution (A) containing a polymerization initiator, a polymerizable monomer, and a polymerization solvent, and a solution (B) containing a catalyst and a polymerization solvent are continuously mixed by a static mixer, The polymerization is carried out by feeding to a mold reactor, but the electron donor is preferably contained in the solution (A).

(Polymerizable monomer)
Examples of the polymerizable monomer used for cationic polymerization include olefins having 3 to 12 carbon atoms, conjugated dienes, vinyl ethers, and aromatic vinyl compounds. Of these, olefins having 3 to 12 carbon atoms and conjugated dienes are preferable. Specific examples include, for example, isobutylene, propylene, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-2-butene, pentene, 4-methyl-1-pentene, hexene, and 5-ethylidene. Norbornene, vinylcyclohexane, butadiene, isoprene, cyclopentadiene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methyl styrene, p-methyl styrene, dimethyl styrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, etc. It is done. Among these, isobutylene, propylene, 1-butene, 2-butene, styrene, p-methylstyrene, α-methylstyrene, indene, isoprene, cyclopentadiene and the like are preferable. In the continuous production method of the present invention, these polymerizable monomers may be used alone or in combination of two or more. In particular, isobutylene is preferable, but in this case, it may be a cationic polymerizable monomer component in combination with other cationic polymerizable monomers other than isobutylene.

(Reaction temperature)
The reaction temperature can be in the range of −100 to 0 ° C. Under relatively high temperature conditions, the reaction rate is slow, and side reactions such as chain transfer reactions occur. Therefore, it is preferable to select a temperature lower than −10 ° C. However, if the reaction temperature is lower than −100 ° C., a substance (raw material or polymer) involved in the reaction may be precipitated. Therefore, a more preferable reaction temperature is −80 to −10 ° C.

  As the reaction temperature control, it is desirable to cool the pressure mixing apparatus for mixing raw materials, the static mixer, and the tubular reactor independently or simultaneously. For example, a pressure-resistant stirring device, a static mixer, and a tubular reactor can be immersed in the refrigerant bath, but not limited thereto.

(Polymerization solvent)
In the method of the present invention, a polymerization solvent may be used, and a single solvent selected from the group consisting of halogenated hydrocarbons, aliphatic hydrocarbons, and aromatic hydrocarbons, or a mixed solvent thereof can be used (Japanese Patent Laid-Open No. Hei 9 (1998)). 8-53514). Examples of halogenated hydrocarbons include chloroform, methylene chloride, 1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride, n-butyl chloride, 1-chloropropane, 1-chloro-2-methylpropane, and 1-chlorobutane. 1-chloro-2-methylbutane, 1-chloro-3-methylbutane, 1-chloro-2,2-dimethylbutane, 1-chloro-3,3-dimethylbutane, 1-chloro-2,3-dimethylbutane, 1-chloropentane, 1-chloro-2-methylpentane, 1-chloro-3-methylpentane, 1-chloro-4-methylpentane, 1-chlorohexane, 1-chloro-2-methylhexane, 1-chloro- 3-methylhexane, 1-chloro-4-methylhexane, 1-chloro-5-methylhexane, 1-chlorohept , 1-chlorooctane, 2-chloropropane, 2-chlorobutane, 2-chloropentane, 2-chlorohexane, 2-chloroheptane, 2-chlorooctane, chlorobenzene, etc., and the solvent selected from these can be used alone Alternatively, it may be composed of two or more components.

  As the aliphatic hydrocarbon, butane, pentane, neopentane, n-hexane, heptane, octane, cyclohexane, methylcyclohexane, and ethylcyclohexane are preferable, and the solvent selected from these may be used alone or in combination of two or more components. It may consist of. Moreover, as aromatic hydrocarbon, benzene, toluene, xylene, and ethylbenzene are preferable, and the solvent selected from these may be single or may be composed of two or more components.

  In particular, a mixed solvent of a halogenated hydrocarbon and an aliphatic hydrocarbon and a mixed solvent of a halogenated hydrocarbon and an aromatic hydrocarbon are more preferably used from the viewpoint of reaction control and solubility.

  In the present invention, the polymerization solvent is preferably a mixed solvent in which a primary and / or secondary monohalogenated hydrocarbon having 3 to 8 carbon atoms and an aliphatic and / or aromatic hydrocarbon are combined. . Furthermore, a mixed solvent of n-butyl chloride and n-hexane is preferable.

  For example, when n-butyl chloride and n-hexane are mixed to form a solvent, the content of n-butyl chloride in the mixed solvent is not particularly limited, but is generally 10 to 100% by weight. More preferably, it can be made into the range of 50 to 100 weight%. When using a mixed solvent as an embodiment of the present invention, considering the solubility of the polymer to be obtained, the viscosity of the solution and the ease of heat removal, the solvent should be adjusted so that the concentration of the polymer is 5 to 90% by weight. From the viewpoint of production efficiency and operability, it is advantageous to use 10 to 70% by weight.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited only to these examples.

Each physical property of the polymer shown in this example was measured by the following method.
(Molecular weight and molecular weight distribution)
Waters GPC system (column: Shodex K-804 (polystyrene gel), Showa Denko KK, mobile phase: chloroform). The number average molecular weight is expressed in terms of polystyrene.

Example 1
After preparing two tanks of 3L pressure-resistant stirrers and replacing the two tanks, the static mixer and the tubular reactor with nitrogen, one pressure-resistant stirrer was used in a polymerization solvent (n-butyl chloride, n-hexane in volume ratio). 9: 1) was mixed, and 2.0 g of p-DCC as a polymerization initiator and 2.014 g of 2-methylpyridine as an electron donor (molar ratio to the polymerization initiator after mixing = 2.5) were used as polymerization solvents. After dissolving in 2 ml, it was put into a pressure-resistant stirrer, and 800 ml of isobutylene was added as a polymerizable monomer. The other pressure-resistant stirrer is charged with 1080 ml of a polymerization solvent (n-butyl chloride and n-hexane mixed at a volume ratio of 9: 1), and 23.8 ml of TiCl ₄ as a catalyst (polymerization initiator after mixing). To the molar ratio = 25). Each apparatus was installed in a refrigerant bath in which the alcohol solution was cooled with dry ice, and both tanks were cooled to -70 ° C. A static mixer and a tubular reactor were also installed in the refrigerant bath and cooled to -70 ° C. Nitrogen was poured into the pressure-resistant stirrer, each was pressurized to 0.25 MPa, and liquid feeding was performed by pressure feeding. The static mixer used was a Noritake Company (model T3-27R-1PT) having a tube diameter of 3.4 mm, a tube length of 155 mm, and 27 elements. The tubular reactor used had an inner diameter of 4 mm and a tube length of 10 m (snaked tube). The average flow velocity in the tube was 0.027 m / s (average residence time was about 6 minutes). The polymer taken out from the outlet of the tubular reactor was deactivated and washed with water, and then the solvent was removed to obtain a polymer.

  The peak molecular weight (Mp), number average molecular weight (Mn), and molecular weight dispersity (Mw / Mn) of the obtained polymer were measured by GPC method. The results are shown in Table 1 below.

(Example 2)
After preparing two tanks of 3L pressure-resistant stirrers and replacing the two tanks, the static mixer and the tubular reactor with nitrogen, one pressure-resistant stirrer was used in a polymerization solvent (n-butyl chloride, n-hexane in volume ratio). 9: 1) was added, and 3.0 g of p-DCC as a polymerization initiator and 3.021 g of 2-methylpyridine as an electron donor (molar ratio to the polymerization initiator after mixing = 2.5) were respectively used as polymerization solvents. After dissolving in 2 ml, it was put into a pressure-resistant stirrer, and 300 ml of isobutylene was added as a polymerizable monomer. The other pressure-resistant stirrer is charged with 570 ml of a polymerization solvent (n-butyl chloride and n-hexane mixed at a volume ratio of 9: 1), and 35.7 ml of TiCl ₄ as a catalyst (polymerization initiator after mixing). To the molar ratio = 25). Each apparatus was installed in a refrigerant bath in which the alcohol solution was cooled with dry ice, and both tanks were cooled to -60 ° C. A static mixer and a tubular reactor were also installed in the refrigerant bath and cooled to -60 ° C. Nitrogen was poured into the pressure-resistant stirrer, each was pressurized to 0.20 MPa, and liquid feeding was performed by pressure feeding. The static mixer used was a Noritake Company (model T3-27R-1PT) having a tube diameter of 3.4 mm, a tube length of 155 mm, and 27 elements. The tubular reactor used had an inner diameter of 4 mm and a tube length of 10 m (snaked tube). The average flow velocity in the tube was 0.27 m / s (average residence time was about 40 seconds). The polymer taken out from the outlet of the tubular reactor was deactivated and washed with water, and then the solvent was removed to obtain a polymer.

  The peak molecular weight (Mp), number average molecular weight (Mn), and molecular weight dispersity (Mw / Mn) of the obtained polymer were measured by GPC method. The results are shown in Table 1 below.

(Comparative Example 1)
After the inside of the polymerization vessel of the 2 L separable flask was purged with nitrogen, 1110 ml of a polymerization solvent (n-butyl chloride and n-hexane were mixed at a volume ratio of 9: 1) was added using a syringe. The polymerization container was placed in a refrigerant bath in which the alcohol solution was cooled with dry ice, and cooled to -70 ° C. After cooling, 0.65 g of p-DCC as a polymerization initiator, 0.288 g of 2-methylpyridine as an electron donor (molar ratio to the polymerization initiator = 1.1), and 300 ml of isobutylene as a polymerizable monomer were added. It was. Finally, the reaction is started by adding 3.4 ml of TiCl ₄ as catalyst (molar ratio to the polymerization initiator = 11). The polymerization reaction was carried out batchwise, and the stirring rotation speed during the polymerization reaction was 500 rpm.

  After a certain period of time, the polymer was sampled, and the peak molecular weight (Mp), number average molecular weight (Mn), and molecular weight dispersity (Mw / Mn) of the polymer were measured by the GPC method. The results are shown in Table 1 below.

  As is clear from Examples 1 and 2 and Comparative Example 1 above, the conventional method (batch method) has a molecular weight dispersity of less than 1.2 in the present production method (continuous method) while it is 1.2 or more. It is excellent in a certain point. As is clear from Example 1 and Comparative Example 1, the reaction time required for 1200 seconds in the conventional method is equivalent to that in 300 seconds in the present production method, and an equivalent polymer is obtained stably thereafter. It is excellent in that it is made.

  Further, as shown in Example 2, in this production method, the molecular weight dispersity was 1.1 immediately after the start of polymerization (60 seconds), whereas in Comparative Example 1, it was 2.0, and in this production method, the polymerization was started. It is also excellent in that the reaction can be controlled immediately after.

1. 1. Nitrogen supply line Pressure mixing device for mixing raw materials (polymerization solvent, polymerization initiator, polymerizable monomer, electron donor)
3. Pressure mixing device for catalyst mixing (polymerization solvent, catalyst)
4). 4. Raw material supply line 5. Catalyst supply line 6. Static mixer Tube reactor

Claims (11)

A solution (A) containing a polymerization initiator, a polymerizable monomer, and a polymerization solvent, and a solution (B) containing a catalyst and a polymerization solvent are separately and continuously supplied to a static mixer to prepare both solutions. after mixing, a method of continuously producing living cationic polymer, characterized in that the polymerization is carried out by supplying to the tubular reactor. The method for continuously producing a living cationic polymer according to claim 1, wherein the solution (A) contains an electron donor. The method for continuously producing a living cationic polymer according to claim 2, wherein the electron donor is present in a molar ratio of 1 to 5 times with respect to the polymerization initiator in the tubular reactor. The continuous production method of a living cationic polymer according to any one of claims 1 to 3, wherein the catalyst is present in a molar ratio of 1 to 50 times with respect to the polymerization initiator in the tubular reactor. The continuous production method of a living cationic polymer according to any one of claims 1 to 4, wherein the average flow velocity in the tube of the solution passing through the tubular reactor is 0.01 to 1 m / s. 6. The method for continuously producing a living cationic polymer according to any one of claims 1 to 5, wherein the ratio L / D between the length L of the tubular reactor and the tube diameter D is 10 or more. The living cationic polymer continuation according to any one of claims 1 to 6, wherein the polymerizable monomer is a cationic polymerizable monomer component containing at least isobutylene, and the catalyst is a Lewis acid catalyst. Production method. The polymerization initiator is (1-chloro-1-methylethyl) benzene, 1,4-bis (1-chloro-1-methylethyl) benzene, and 1,3,5-tris (1-chloro-1-methyl). The method for continuously producing a living cationic polymer according to any one of claims 1 to 7, wherein the method is at least one compound selected from the group consisting of ethyl) benzene. 2. The polymerization solvent is a mixed solvent in which a primary and / or secondary monohalogenated hydrocarbon having 3 to 8 carbon atoms and an aliphatic and / or aromatic hydrocarbon are combined. The continuous manufacturing method of the living cationic polymer in any one of -8. The continuous production method of a living cationic polymer according to any one of claims 1 to 9, wherein the polymerization solvent is a mixed solvent of n-butyl chloride and n-hexane. The continuous production method of the living cationic polymer according to any one of claims 1 to 10, wherein the polymerization temperature is -80 to -10 ° C.

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