JP2012172112A - Process for continuously manufacturing isobutylene based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a continuous manufacturing process which has a narrow residence time distribution to inhibit side reactions and can obtain a living cationic polymer of the same structure as designed with a small degree of dispersion in continuously carrying out the living cationic polymerization reaction.SOLUTION: In the manufacturing process for carrying out the polymerization of polymerizable monomers by continuously supplying a solution (A) including a polymerization initiator, a first polymerizable monomer, and a polymerization solvent and a solution (B) including a Lewis acid catalyst and a polymerization solvent to a first mixing section and successively to a first reaction section connected with the first mixing section, the inner diameter of the reaction section is set at 1 mm or more and the inner diameter D (mm) of the first mixing section and the flow rate U (m/sec) in the first mixing section is set in the range meeting the formula (1): 50>D×U>0.3.

Description

  The present invention relates to a continuous process for producing an isobutylene polymer by living cationic polymerization.

  Living polymerization means, in a narrow sense, polymerization in which the molecular growth end always keeps its activity and the molecular chain grows, but in general, the polymerization growth end is inactivated and activated. Also included is pseudo-living polymerization in which molecular chains grow while they are in equilibrium. 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. The isobutylene polymer obtained by living cationic polymerization is industrially useful because it enables structural control such as introduction of a functional group at the terminal. An isobutylene block copolymer obtained by copolymerizing isobutylene and a polymerizable monomer component having a high Tg (glass transition point) is a thermoplastic elastomer, which is also industrially useful.

  As described in Patent Document 1 and Patent Document 2, the living cation polymerization reaction is operated using a stirred tank type polymerizer, and a large number of reports are conducted in a batch system by charging reaction raw materials into the polymerizer. Occupy. However, considering industrial mass production, the batch system has many problems as described later.

  In the batch polymerization method, it is necessary to increase the size of the polymerization vessel in order to improve productivity. When the size is increased, it is necessary to devise a method for increasing the heat removal area by using an internal snake tube cooling method, an external heat exchanger circulation method, a reflux condenser method, etc. In this case, the equipment cost is increased due to the increase in size and complexity of the heat removal equipment. Will soar. When trying to suppress the equipment cost, it becomes difficult to control the internal temperature, and side reactions increase, resulting in problems that it is difficult to obtain a polymer having a low degree of dispersion that is characteristic of living polymerization. In order to avoid the problem of heat removal equipment, semi-batch polymerization methods such as sequential addition of monomers may be used, but the initial monomer concentration is less than batch type, and side reactions are likely to occur. There is a problem of being bad.

  On the other hand, with the aim of improving productivity, a continuous polymerization method in which raw materials are continuously supplied to a polymerization vessel has been studied. 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 type polymerizer. 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. Yes. In Patent Documents 5, 6, and 7, in conducting living cationic polymerization of isobutylene, the raw material is continuously supplied to the flow-type stirred tank type polymerizer to start the polymerization, and then continuously supplied to the flow-tube type polymerizer. Living cationic polymerization proceeds. In Patent Document 8, raw materials are supplied from two flow paths, and a static mixer (a tubular mixer incorporating one or more static mixers composed of a large number of mixing elements) and a tubular polymerizer are circulated in series. Living cationic polymerization of isobutylene is performed. In Patent Document 9, various living cationic polymerizations can be performed by continuously joining raw materials to start a reaction and then allowing the reaction liquid to flow through a narrow channel.

  However, some problems remain in carrying out continuous polymerization. In Patent Document 3, as a result of continuous polymerization in one stirred tank type polymerizer, the resulting polymer has a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.4 to 1.8. , Which is greater than the degree of dispersion in batch polymerization. In such a tendency, when continuous polymerization is performed in one stirred tank, the residence time of the reaction liquid has a wide distribution (that is, the residence time in the tank varies depending on the polymer molecules). This is considered to be due to the fact that the lengths of molecules grown by polymerization are not uniform. 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 distribution of the residence time of the reaction solution is considered to be very narrow because a tubular polymerization apparatus is used, the degree of dispersion of the obtained polymer is as large as 3.1. In Patent Documents 5, 6, and 7, the dispersion degree is improved by 1.2 to 1.3 by passing through a tubular polymerization apparatus after passing through one stirring tank polymerization apparatus. Since the tank is used, if scale-up is performed to improve productivity, problems remain in terms of complicated mixing conditions in the tank, side reaction control, and heat removal efficiency. In Patent Document 8, there remains a problem that a large amount of static mixer is required for large-scale production. Further, in Patent Document 9, only a polymer having a molecular weight of about several thousand is obtained, and it is presumed that there are problems such as blockage accompanying an increase in viscosity due to polymerization. Since a polymer having a molecular weight of about 5,000 to 300,000 is considered industrially useful, it is a problem that a polymer having a large molecular weight cannot be obtained.

  As described above, when using a stirred tank type polymerization tank, there is a concern about the spread of residence time distribution and scale-up, and when using a tube type polymerization apparatus, mixing is insufficient immediately after the raw material is supplied to the polymerization apparatus. There are concerns. Among various polymerization reactions, the living cationic polymerization of isobutylene-based polymers controls the initiation reaction by applying special measures to the catalyst and additives, and if the temperature is not low, the polymerization activity decreases or side reactions occur simultaneously. Therefore, it is presumed that it was relatively difficult to apply continuous polymerization, for example, it was important to remove the heat of polymerization 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 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 particularly important problems in the continuous polymerization method of living polymers.

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 JP 2010-241908 A JP 2008-001771 A

  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 living polymer having a low degree of dispersion. Another object of the present invention is to provide a continuous production method of a living polymer that can be carried out by a compact facility that can effectively control the internal temperature of the polymerization vessel. A further object of the present invention is to provide a continuous production method capable of obtaining a living polymer in which functional groups are introduced at the terminals and the synthesis of block copolymers is as originally designed.

In the present invention, a solution (A) containing a polymerization initiator, a first polymerizable monomer, and a polymerization solvent is continuously mixed with a solution (B) containing a Lewis acid catalyst and a polymerization solvent. In the manufacturing method of polymerizing a polymerizable monomer by supplying to the first reaction section and subsequently supplying the first reaction section connected to the first mixing section, the inner diameter of the reaction section is 1 mm or more, and the first The present invention relates to a method for producing an isobutylene polymer, characterized in that the inner diameter D (mm) of the mixing portion and the flow velocity U (m / sec) in the first mixing portion are in a range satisfying the relationship of the following formula (1). .
50> D × U> 0.3 (1)

  Preferably, the internal diameter of a 1st reaction part is 1 mm-10 mm, It is related with the manufacturing method of the isobutylene type polymer of Claim 1 characterized by the above-mentioned.

  Preferably, the present invention relates to a method for producing an isobutylene polymer, wherein the solution (A) contains an electron donor.

Preferably, the present invention relates to a method for producing an isobutylene polymer, wherein the electron donor is present in a molar ratio of 0.2 to 10 times the polymerization initiator in the first reaction part.
Preferably, the present invention relates to a method for producing an isobutylene polymer, wherein the Lewis acid catalyst is present in a molar ratio of 10 to 300 times with respect to the polymerization initiator in the first reaction part.

  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 process for producing an isobutylene polymer, which is at least one compound selected from the group consisting of (1-methylethyl) benzene.

  Preferably, the present invention relates to a method for producing an isobutylene polymer, wherein the ratio of the length and the inner diameter of the first reaction part (length / inner diameter) is 10 or more.

  Preferably, the reaction liquid that has passed through the first reaction unit and the functional group introduction substance are continuously supplied to the second mixing unit, and then supplied to the second reaction unit connected to the mixing unit, A method for producing an isobutylene polymer, comprising reacting a group-introducing substance.

  Preferably, the present invention relates to a method for producing an isobutylene polymer, wherein the functional group-introducing substance is allyltrimethylsilane.

  The reaction solution that has passed through the first reaction section described above and the second polymerizable monomer are continuously supplied to the second mixing section, and subsequently to the second reaction section connected to the mixing section. It is related with the manufacturing method of the isobutylene type block copolymer characterized by supplying and polymerizing a 2nd polymerizable monomer.

  Preferably, the present invention relates to a method for producing an isobutylene polymer, wherein the inner diameter of the second reaction part is 2 mm to 20 mm.

  Preferably, one of the first polymerizable monomer and the second polymerizable monomer is a monomer mainly containing isobutylene, and the other one is a monomer containing mainly an aromatic vinyl monomer. It is related with the manufacturing method of the isobutylene type block copolymer characterized by being a body component.

  Preferably, the present invention relates to a process for producing an isobutylene block copolymer, wherein the ratio of the length and the inner diameter of the second reaction part (length / inner diameter) is 10 or more.

  Preferably, the reaction solution that has passed through the second reaction section and the functional group-introducing substance are continuously supplied to the third mixing section and subsequently supplied to the third reaction section connected to the mixing section. And a method for producing an isobutylene block copolymer, which comprises reacting a functional group-introducing substance.

  Preferably, the present invention relates to a process for producing an isobutylene block copolymer, wherein the functional group-introducing substance is allyltrimethylsilane.

  By the continuous production method of the present invention, the residence time can be kept constant (narrow residence time distribution), and side reactions can be controlled, so that the degree of dispersion of the resulting isobutylene polymer is small, It is also effective in that it has excellent mechanical properties.

An example (schematic diagram) of a continuous production apparatus for isobutylene polymer used in the present invention An example (schematic diagram) of an apparatus for continuous production of isobutylene block copolymers or functionalized isobutylene polymers used in the present invention

(Applicable reaction systems)
The production method of the present invention is suitable for a living polymerization reaction and is further effective for living cationic polymerization. Details of the living cationic polymerization will be described below. As the living cationic polymerization, for example, synthesis described in JP Kennedy et al. (Carbocationic Polymerization, John Wiley & Sons, 1982) or K. Matyjaszewski et al. (Cationic Polymerizations, Marcel Dekker, 1996) can be applied.

(Polymerization apparatus and method)
The greatest feature of the present invention is that a solution (A) containing a polymerization initiator, a first polymerizable monomer, and a polymerization solvent is continuously added to a solution (B) containing a Lewis acid catalyst and a polymerization solvent. In the production method for polymerizing a polymerizable monomer by supplying to the first mixing section and subsequently supplying to the first reaction section connected to the first mixing section, the inner diameter of the reaction section is 1 mm or more, And it is making the internal diameter D (mm) of a 1st mixing part and the flow velocity U (m / sec) in a 1st mixing part into the range satisfy | filling the relationship of following formula (1).
50> D × U> 0.3 (1)

  An isobutylene polymer is industrially useful as a polymer having a molecular weight of about several thousand to several tens of thousands, but a reaction solution containing a polymer having such a molecular weight has a high viscosity. Therefore, if the inner diameter of the reaction section is less than 1 mm when the reaction section is circulated, there are restrictions such as special pumps that can send liquids, or the reaction section may be blocked due to high viscosity. Due to problems, only low molecular weight polymers can be polymerized. Therefore, by setting the inner diameter of the reaction part to 1 mm or more, it becomes possible to obtain a polymer having a molecular weight of about several thousand to several tens of thousands. However, since the heat transfer area per volume of the reaction part is reduced when the inner diameter of the reaction part is increased, the heat removal performance is lowered.

  At the same flow rate, when the inner diameter D (mm) of the first mixing portion increases, the flow velocity U (m / sec) in the first mixing portion decreases. If the flow rate U (m / sec) in the first mixing section becomes too small, the supplied solution (A) and solution (B) are not sufficiently mixed and the reaction is not controlled. On the other hand, if the inner diameter D (mm) of the first mixing section is too small to increase the flow velocity U (m / sec) in the first mixing section in order to ensure sufficient mixing, there is a problem of blockage or special Such as the need for a simple liquid pump.

As described above, when the inner diameter D (mm) of the first mixing portion changes at the same flow rate, the flow velocity U (m / sec) in the first mixing portion also changes. That is, there is a correlation between the inner diameter D (mm) of the mixing portion and the flow velocity U (m / sec) in the first mixing portion, and a preferable value is expressed as a range that satisfies the relationship of the following formula (1).
50> D × U> 0.3 (1)

  When D × U is larger than 50, there is a problem that a very large reaction volume is required to complete the reaction or a liquid feed pump with a very high discharge pressure is required. There is a problem in that the quality is lowered due to the occurrence of many.

  In the method of the present invention, the reaction solution that has passed through the first reaction section and the second polymerizable monomer are continuously supplied to the second mixing section and subsequently connected to the mixing section. Then, the second polymerizable monomer is polymerized by supplying it to the reaction section, and an isobutylene block copolymer can be obtained. When mixing the second polymerizable monomer, it is preferable that the first polymerizable monomer is substantially consumed. Since the viscosity is increased by using the block copolymer, the inner diameter of the second reaction part is preferably 2 mm or more, and preferably 20 mm or less from the viewpoint of heat removal performance.

  The ratio of the length and the inner diameter of the first reaction part (length / inner diameter) and the ratio of the length and the inner diameter of the second reaction part are preferably 10 or more. If the ratio is too small, the heat transfer area necessary for heat removal may be insufficient. Further, the residence time of the reaction solution is insufficient, and polymerization may be incomplete.

  The heat removal structure of the mixing part and the reaction part is not particularly limited as long as the required heat removal performance is exhibited, and the mixing part and the reaction part may be directly immersed in the cooling bath, A heat exchange may be performed by providing a jacket structure in the mixing part and the reaction part and passing a refrigerant through the jacket.

  After the obtained reaction solution has deactivated the catalyst contained in water, alcohols, etc., for example, the two phases are separated, the organic phase is washed with water if necessary, and the organic solvent is distilled off to distill off the organic solvent. Coalescence can be obtained.

(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 if the molecular weight is too short, the properties of the isobutylene polymer such as rubber elasticity and thermoplasticity will not be exhibited, which is industrially beneficial. From the viewpoint of a new material, it is usually 5,000 to 500,000, more preferably 10,000 to 300,000.

(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.)

  As the polymerization initiator, (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 TCC) is preferred. 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.

(Lewis acid catalyst)
The catalyst used for 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 the Lewis acid catalyst used is preferably 10 to 300 times the molar amount of the polymerization initiator in the first reaction part. When the amount of the Lewis acid catalyst is too small, the polymerization reaction rate is remarkably suppressed, and a long time is required for the cationic polymerization reaction, resulting in a decrease in productivity. Conversely, if there are too many Lewis acid catalysts, side reactions tend to increase, and the degree of dispersion increases due to the occurrence of proton initiation reactions and chain transfer reactions.

(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 a molar ratio of 0.2 to 10 times the polymerization initiator in the first reaction part. 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 a long time is required for the cationic polymerization reaction, resulting in a decrease in productivity. In the present invention, a solution (A) containing a polymerization initiator, a first polymerizable monomer, and a polymerization solvent, and a solution (B) containing a Lewis acid catalyst and a polymerization solvent are continuously added to the first solution. It is characterized in that the polymerizable monomer is polymerized by supplying it to the mixing unit and subsequently supplying it to the first reaction unit connected to the first mixing unit, but the catalyst and the electron donor are mixed in advance. Then, since there is a possibility of precipitation, the electron donor is preferably contained in the solution (A).

(Polymerizable monomer)
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 Lewis acid catalyst.

  When obtaining an isobutylene polymer, the first polymerizable monomer component is a monomer mainly containing isobutylene. “Mainly” means that containing 30% or more of isobutylene, and preferably containing 50% or more.

  When obtaining an isobutylene block copolymer, at least one of the first polymerizable monomer component or the second polymerizable monomer component is a monomer mainly containing isobutylene, and the second polymerizable monomer The body component has a different compound and / or composition from the first polymerizable monomer component.

  As the monomers other than isobutylene of the first polymerizable monomer component and the second polymerizable monomer component, polymerizable monomers that can be applied in various polymerization systems described below are used without particular limitation. be able to.

  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, propylene, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-2-butene, pentene, 4-methyl-1-pentene, hexene, 5-ethylidene norbornene, Examples include 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, and indene. Among these, isobutylene, propylene, 1-butene, 2-butene, styrene, p-methylstyrene, α-methylstyrene, indene, isoprene, cyclopentadiene and the like are preferable. In the case of an isobutylene block copolymer, at least one of the first polymerizable monomer and the second polymerizable monomer is a monomer component mainly containing isobutylene, but one is mainly aromatic vinyl. It is preferable that it is a monomer component containing a system monomer.

In the case of an isobutylene-based polymer, the reaction solution and the functional group introduction substance that have passed through the first reaction section are continuously supplied to the second mixing section, and subsequently connected to the mixing section. The isobutylene-based polymer having a functional group may be obtained by reacting the functional group-introducing substance to the reaction part, and in the case of an isobutylene-based block copolymer, the reaction solution that has passed through the second reaction part And functional group-introducing substance are continuously supplied to the third mixing part and subsequently supplied to the third reaction part connected to the mixing part, and the functional group-introducing substance is reacted to cause the isobutylene system having a functional group A block copolymer may be obtained.
The functional group-introducing substance here is for introducing a functional group into the obtained polymerization terminal, and it is preferable to use allyltrimethylsilane from the viewpoint of reactivity and usefulness of the obtained polymer.

(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, and it is not economical to implement industrially. Therefore, a more preferable reaction temperature is −80 to −10 ° C.

(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. 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. Among them, 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 is combined is preferable. Furthermore, a mixed solvent of n-butyl chloride and n-hexane is preferable.

  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.

The polymer shown in this example was analyzed by the method shown below.
(Analysis of 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.
(Analysis of molecular chain end structure)
The molecular chain terminal structure was determined by measuring and comparing the resonance signals of protons belonging to each structure by 1H-NMR (400 MHz).
(Measurement of breaking strength)
The value of the breaking strength is obtained by punching a 2 mm thick press sheet into a dumbbell No. 3 type and performing a tensile test in accordance with JIS K 6251.

Example 1
The outline of the apparatus is shown in FIG. Specifically, after preparing two pressure-resistant tanks with a capacity of 3 L and replacing the two pressure-resistant tanks and the tubular polymerizer with nitrogen, one tank is filled with a polymerization solvent (n-butyl chloride, n-hexane). (Mixed at a ratio of 9: 1) is 1080 ml, p-DCC is 1.92 g as a polymerization initiator, and 2-methylpyridine is added as an electron donor so that the molar ratio with respect to the polymerization initiator in the reaction part is 6. Then, 470 ml of isobutylene was added as the first polymerizable monomer. In the other pressure tank, 1400 ml of a polymerization solvent (n-butyl chloride and n-hexane mixed at a volume ratio of 9: 1) and a molar ratio with respect to the polymerization initiator after mixing TiCl ₄ as a catalyst were 200 It was thrown to become. Cooling was performed by immersing two pressure tanks and a polymerization vessel in a cooling bath at -50 ° C. A T-shaped mixer having an inner diameter of 1.3 mm was used for the mixing portion of the polymerization vessel, and a single tube having an inner diameter of 3 mm and a tube length of 10 m was used for the reaction portion. The T-shaped mixer was supplied with an isobutylene solution and a catalyst solution at 35 ml / min, respectively. The catalyst in the reaction solution collected from the outlet of the polymerization vessel 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 dispersity (Mw / Mn) of the obtained polymer were measured by GPC method. Moreover, the terminal structure of the obtained polymer was measured by NMR. In NMR, the terminal olefination rate of a polymer molecular chain is measured. Since terminal olefination is caused by a side reaction, it is 0 for complete living polymerization, and this value is increased if there are many side reactions. Table 1 shows the results.

(Example 2)
In Example 1, 2-methylpyridine was added as an electron donor so that the molar ratio with respect to the polymerization initiator in the reaction part was 1, and a T-shaped mixer having an inner diameter of 3 mm was installed at the junction part of the tubular polymerization apparatus. It was the same except that it was used. Table 1 shows the results.

(Example 3)
In Example 2, TiCl ₄ was mixed as a catalyst so that the molar ratio with respect to the polymerization initiator after mixing was 180, a single tube having an inner diameter of 2 mm and a tube length of 10 m was used for the reaction part, and the T-shaped mixer was used. It was the same except that the isobutylene solution and the catalyst solution were respectively supplied at 30 ml / min. Table 1 shows the results.

Example 4
Of Example 1, the reaction part was the same as Example 1 except that a single tube having an inner diameter of 3 mm and a tube length of 5 m was used. Table 1 shows the results.

(Example 5)
In Example 4, it was the same except that the isobutylene solution and the catalyst solution were respectively supplied to the T-shaped mixer at 30 ml / min. Table 1 shows the results.

(Example 6)
In Example 4, it was the same except that the isobutylene solution and the catalyst solution were respectively supplied to the T-shaped mixer at 35 ml / min. Table 1 shows the results.

(Example 7)
In Example 4, 2-methylpyridine was added as an electron donor so that the molar ratio with respect to the polymerization initiator in the reaction part was 5, and an isobutylene solution and a catalyst solution were respectively supplied to a T-shaped mixer at 27 ml / min. It was the same except that. Table 1 shows the results.

(Example 8)
In Example 7, it was the same except that the isobutylene solution and the catalyst solution were respectively supplied to the T-shaped mixer at 38 ml / min. Table 1 shows the results.

(Comparative Example 1)
After the inside of the 2 L separable flask was purged with nitrogen, 491 ml of a polymerization solvent (n-butyl chloride and n-hexane were mixed at a volume ratio of 9: 1) was added. A separable flask was placed in a refrigerant bath in which the alcohol solution was cooled with dry ice, and cooled to −50 ° C. After cooling, 0.49 g of p-DCC as a polymerization initiator and 2-methylpyridine as an electron donor were added so that the molar ratio to the polymerization initiator was 1, and 140 ml of isobutylene was added as a polymerizable monomer. . Finally, the polymerization reaction was started by adding TiCl ₄ as a catalyst so that the molar ratio with respect to the polymerization initiator was 20. The polymerization reaction was carried out batchwise, and the stirring rotation speed during the polymerization reaction was 500 rpm. Table 1 shows the results.

(Comparative Example 2)
In Example 1, 2-methylpyridine was added so that the molar ratio with respect to the polymerization initiator in the reaction part was 1, and the molar ratio with respect to the polymerization initiator after mixing TiCl ₄ as a catalyst was 72. The same procedure was performed except that a T-shaped mixer having an inner diameter of 8.6 mm was used for the mixing portion of the tubular polymerizer, and the isobutylene solution and the catalyst solution were respectively supplied to the T-shaped mixer at 25 ml / min. Table 1 shows the results.

(Comparative Example 3)
In Comparative Example 2, the T mixer was the same except that the isobutylene solution and the catalyst solution were respectively supplied at 20 ml / min. Table 1 shows the results.

(Comparative Example 4)
In Comparative Example 2, 2-methylpyridine was added so that the molar ratio with respect to the polymerization initiator in the reaction part was 6, and the molar ratio with respect to the polymerization initiator after mixing TiCl ₄ as a catalyst was 200. It was the same except that the isobutylene solution and the catalyst solution were respectively supplied to the T-shaped mixer at 30 ml / min. Table 1 shows the results.

As is clear from the above Examples and Comparative Example 1, in the conventional batch method, the dispersity is as high as 1.5 or more, whereas in the continuous production method of the present invention, the dispersity is as small as less than 1.3. It is excellent in that it can be controlled. Further, as is clear from the examples and comparative examples 2 to 4, the relationship between the inner diameter D (mm) of the first mixing portion and the flow velocity U (m / sec) in the first mixing portion is expressed by the following formula (1). If the range is not within the range, the terminal olefin ratio is as high as 10% or more.
50> D × U> 0.3 (1)

Example 9
An outline of the apparatus is shown in FIG. Specifically, a T-shaped mixer having an inner diameter of 8.6 mm was used for the second mixing portion, and a single tube having an inner diameter of 4.35 mm and a tube length of 2 m was used for the second reaction portion. The pressure-resistant tank for the second polymerizable monomer was purged with nitrogen, and 151 ml of styrene was charged. Polymerization of the first polymerizable monomer was performed under the same conditions as in Example 7, and subsequently, styrene was used as the second polymerizable monomer in the second mixing portion with respect to the first polymerizable monomer. The molar ratio was 0.174. The catalyst in the reaction solution collected from the outlet of the polymerization vessel 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 dispersity (Mw / Mn) of the obtained polymer were measured by GPC method. Further, the mechanical strength of the obtained polymer was measured. If the first monomer polymer and the second monomer polymer are block copolymerized, the mechanical strength is increased, but if the block copolymer is not copolymerized, the mechanical strength is decreased. In some cases, the measurement itself is impossible. Table 2 shows the results.

(Example 10)
Polymerization of the first polymerizable monomer was performed under the same conditions as in Example 8, and subsequently styrene was used as the second polymerizable monomer in the second mixing portion with respect to the first polymerizable monomer. The molar ratio was 0.174. Table 2 shows the results.

(Comparative Example 5)
Before the solution polymerized in Comparative Example 1 was deactivated, styrene was subsequently added as a polymerizable monomer so that the molar ratio with respect to the first polymerizable monomer was 0.174. The polymerization reaction was carried out batchwise, and the stirring speed during the polymerization reaction was 500 rpm. Table 2 shows the results.

(Comparative Example 6)
The first polymerizable monomer is polymerized under the same conditions as in Comparative Example 2, and subsequently, styrene is used as the second polymerizable monomer in the second mixing portion with respect to the first polymerizable monomer. The molar ratio was 0.174. Table 2 shows the results.

(Comparative Example 7)
The first polymerizable monomer was polymerized under the same conditions as in Comparative Example 3, and subsequently, styrene was used as the second polymerizable monomer in the second mixing portion with respect to the first polymerizable monomer. The molar ratio was 0.174. Table 2 shows the results.

As apparent from the above Examples and Comparative Example 5, in the conventional batch polymerization, the mechanical strength is as low as 1 MPa or less and the performance as a block copolymer is low, whereas in the production method of the present invention, the mechanical strength is 4 MPa. It is excellent in the point that the performance as a block copolymer becomes high as mentioned above. Further, as is clear from Examples and Comparative Examples 6 and 7, the inner diameter D (mm) of the first mixing portion and the flow velocity U (m / sec) in the first mixing portion are expressed by the following formula (1). If the range does not satisfy the range, the mechanical strength is as low as 1 MPa or less, and the performance as a block copolymer is low. It is excellent in terms of high performance.
50> D × U> 0.3 (1)

1. 1. First pressure-resistant tank for polymerizable monomer 2. Pressure-resistant tank for catalyst 3. Liquid feed pump First mixing unit 5. First reaction part 6. 6. Second pressure resistant tank for polymerizable monomer Second mixing unit 8. Second reaction part

Claims (15)

A solution (A) containing a polymerization initiator, a first polymerizable monomer, and a polymerization solvent, and a solution (B) containing a Lewis acid catalyst and a polymerization solvent are continuously supplied to the first mixing section. Then, in the production method of polymerizing the polymerizable monomer by continuously supplying the first reaction unit connected to the first mixing unit, the inner diameter of the reaction unit is 1 mm or more, and the first mixing unit A method for producing an isobutylene polymer, characterized in that the inner diameter D (mm) and the flow velocity U (m / sec) in the first mixing part are in a range satisfying the relationship of the following formula (1).
50> D × U> 0.3 (1) 2. The method for producing an isobutylene polymer according to claim 1, wherein the inner diameter of the first reaction part is 1 mm to 10 mm. The method for producing an isobutylene polymer according to claim 1 or 2, wherein the solution (A) contains an electron donor. The isobutylene polymer according to any one of claims 1 to 3, wherein the electron donor is present in a molar ratio of 0.2 to 10 times that of the polymerization initiator in the first reaction part. Production method. 5. The method for producing an isobutylene polymer according to claim 1, wherein the Lewis acid catalyst is present in a molar ratio of 10 to 300 times with respect to the polymerization initiator in the first reaction part. . 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 producing an isobutylene polymer according to any one of claims 1 to 5, which is at least one compound selected from the group consisting of ethyl) benzene. The method for producing an isobutylene polymer according to any one of claims 1 to 6, wherein the ratio (length / inner diameter) of the length and the inner diameter of the first reaction part is 10 or more. The reaction solution that has passed through the first reaction section and the functional group introduction substance are continuously supplied to the second mixing section, and subsequently supplied to the second reaction section connected to the mixing section, and the functional group introduction substance is supplied. The process for producing an isobutylene polymer according to claim 1, wherein: The method for producing an isobutylene polymer according to claim 8, wherein the functional group-introducing substance is allyltrimethylsilane. The reaction solution that has passed through the first reaction section according to claim 1 and the second polymerizable monomer are continuously supplied to the second mixing section and subsequently connected to the mixing section. A method for producing an isobutylene block copolymer, wherein the second polymerizable monomer is polymerized by supplying to the reaction part. The method for producing an isobutylene-based block copolymer according to claim 10, wherein the inner diameter of the second reaction part is 2 mm to 20 mm. One of the first polymerizable monomer and the second polymerizable monomer is a monomer mainly containing isobutylene, and the other one is a monomer component mainly containing an aromatic vinyl monomer. The method for producing an isobutylene block copolymer according to claim 10 or 11, wherein: The method for producing an isobutylene block copolymer according to any one of claims 10 to 12, wherein the ratio (length / inner diameter) of the length and the inner diameter of the second reaction part is 10 or more. The reaction solution that has passed through the second reaction part and the functional group-introducing substance are continuously supplied to the third mixing part, and subsequently supplied to the third reaction part connected to the mixing part. The method for producing an isobutylene block copolymer according to any one of claims 10 to 13, wherein the introduced substance is reacted. The method for producing an isobutylene block copolymer according to claim 14, wherein the functional group-introducing substance is allyltrimethylsilane.

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