JP6513953B2 - Method of producing polymer - Google Patents

Description

  The present invention relates to a continuous process by living cationic polymerization.

  Living polymerization, in a narrow sense, refers to polymerization in which the growth end of the polymerization continues to keep 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 the molecular chain grows while being in equilibrium. In such living polymerization, a polymer having a low degree of dispersion is obtained if the polymerization reaction simultaneously starts, and a specific functional group is introduced into the active end of the polymer, or two or more monomers are used. The copolymer can be synthesized by

  Examples of industrially practiced living polymerization include living cationic polymerization of isobutylene described in Patent Document 1 and Patent Document 2. An isobutylene-based polymer obtained by living cationic polymerization is industrially useful because it enables structural control such as introduction of a functional group at an end. In addition, an isobutylene-based block copolymer obtained by copolymerizing isobutylene and a high Tg (glass transition point) polymerizable monomer component becomes a thermoplastic elastomer, which is also industrially useful. Among the various polymerization reactions, living cationic polymerization of isobutylene polymers applies specific measures to additives such as a catalyst and an electron donor to control the initiation reaction, or the polymerization activity decreases unless the temperature is low. Since heat side reactions occur simultaneously, heat removal from the polymerization reaction heat is important. Among the problems with side reactions, not only the degree of dispersion of the polymer increases but also the growth end of the polymer is not controlled, so the introduction of functional groups to the end of the polymer and the synthesis of the block are as originally designed. There is a problem that it does not become. These are particularly important problems in continuous polymerization processes of living polymers.

  As described in Patent Document 1 and Patent Document 2, the operation mode of the living cationic polymerization reaction is mostly a report example carried out in a batch system by charging a reaction raw material into a polymerizer using a stirred tank type polymerizer. Occupy However, considering the industrial mass production, there are many problems in the batch system as described later. In the batch polymerization method, it is necessary to increase the size of the polymerization vessel in order to improve the productivity. If the size is increased, it is necessary to devise a method to increase the heat removal area by the internal flexible tube cooling method, the external heat exchanger circulation method, the reflux condenser method, etc. In this case, the facility cost is increased due to the enlargement and complexity of the heat removal facility. Soaring. If the equipment cost is to be reduced, internal temperature control becomes difficult, and side reactions increase, which causes a problem that it is difficult to obtain a polymer having a small degree of dispersion, which is a feature of living polymerization. In order to avoid the problem of heat removal equipment, semi-batch type polymerization method such as sequential addition of monomers may be used, but the initial monomer concentration is thinner compared to batch type, so side reaction tends to occur, productivity is There is a problem of being bad.

  On the other hand, in order to improve productivity, studies are being made on a continuous polymerization method in which a raw material is continuously supplied to a polymerization vessel. For example, Patent Document 3 attempts a method of performing living cationic polymerization by continuously supplying a polymerization initiator, a Lewis acid catalyst and isobutylene to a single stirred tank polymerizer. In performing living cationic polymerization of isobutylene in Patent Documents 4, 5 and 6, the raw materials are continuously supplied to a flow type stirring tank type polymerizer to start polymerization, and then continuously supplied to a flow pipe type polymerizer. The living cationic polymerization is progressing. However, several problems remain when conducting continuous polymerization. In patent document 3, as a result of performing continuous type polymerization with one stirring tank type polymerizer, the degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of the obtained polymer is 1.4 to 1.8. And the degree of dispersion in batch polymerization. Such a tendency is due to the fact that when continuous polymerization is performed 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 molecule of the polymer), so living It is believed that the influence is that the lengths of the molecules grown by polymerization are not uniform. In Patent Documents 4, 5 and 6, the degree of dispersion is improved in terms of the degree of dispersion of 1.2 to 1.3 by passing through a tubular polymerizer after passing 1 unit of a stirring tank type polymerizer, but stirring Since the tank is used, if scale-up is performed to improve productivity, problems remain in terms of complication of mixing conditions in the tank, side reaction control, and heat removal efficiency.

  As a continuous polymerization method which does not use a stirring tank type polymerizer, in Patent Document 7, after conducting a continuous living cationic polymerization of isobutylene using a shell-and-tube type heat exchanger, the polymer ends in a tubular reactor. Proposed a method to introduce a vinyl group to However, in Patent Document 7, the degree of dispersion of the obtained polymer is as large as 3.1, and the reaction can not be controlled.

  In recent years, microreactor technology that performs processing by passing a fluid through a fine channel has attracted attention. The microreactor technology has features such as high heat removal performance due to the large surface area per unit volume, high-speed mixing performance due to the fine flow path, and high residence time controllability. In the polymerization reaction, it is effective to make use of the high heat removal performance of the microreactor because the heat generated by the reaction is significant. Furthermore, in living polymerization, it is effective to take advantage of the high-speed mixing property and residence time controllability of the microreactor to obtain a polymer of narrow molecular weight distribution. In addition, taking advantage of the features of these microreactors, using a catalyst with high activity for the reaction, or using a large amount of catalyst, or changing the reaction temperature, etc., shorts by speeding up the reaction. The completion of the reaction at the reaction time can be enabled.

  In Patent Document 8, it is supposed that various kinds of living cationic polymerization can be carried out by continuously joining the raw materials to start the reaction and subsequently circulating the reaction solution in a thin flow path. The microreactor technology is also applied to living cationic polymerization of isobutylene, and continuous polymerization methods using a flow path tubular reactor with a flow path diameter of several mm have been studied. In Patent Document 9, a raw material is 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 made to flow in series. Living cationic polymerization of isobutylene is performed. In Patent Document 10, living cationic polymerization of isobutylene at a high temperature is continuously carried out by using a large amount of catalyst while controlling the liquid transfer conditions without using a static mixer. In patent document 11, living cationic polymerization of isobutylene at a high temperature is continuously carried out by using a stacked reactor and using a large amount of catalyst as compared with the conventional method.

  However, in Patent Document 8, it is presumed that only a polymer having a molecular weight of about several thousand can be obtained by using a channel having a channel diameter of 1 mm or less, and there are problems such as blockage due to the increase in viscosity due to polymerization. . Since polymers having a molecular weight of about 5,000 to 300,000 are considered to be industrially useful, it is a problem that a polymer having a large molecular weight can not be obtained. In Patent Document 9, the molecular weight distribution is 1.2 or less but can only be achieved at a low temperature of −70 to −60 ° C., which is a problem in that the heat removal equipment cost and the running cost of the heat removal equipment are high. . In Patent Documents 10 and 11, by using a large amount of catalyst, it is possible to obtain a polymer having a degree of dispersion of about 1.3 under high temperature conditions of -50 ° C using only a tubular reactor. Polymerization under high temperature conditions is advantageous in industrial production because the equipment cost of heat removal equipment for preparing a low temperature environment and the running cost for cooling can be reduced. However, a large amount of catalyst is added to speed up the reaction, and the polymer concentration in the resulting polymerization solution is low, which causes a serious problem in industrial production.

  As described above, in the case of using the stirring tank type polymerization tank, there is a concern about the spread and scale-up of the residence time distribution. Even in continuous polymerization in which a stirring tank type polymerization tank and a tubular reactor are combined, the problems resulting from the stirring tank type polymerization tank are present similarly.

  As described above, when living polymerization is continuously performed using only a tubular reactor including a microreactor, reaction control and speeding up can be achieved within the constraints of equipment cost, running cost, and main auxiliary material cost. It is inferred that establishing a practical continuous polymerization technique was difficult because

Unexamined-Japanese-Patent No. 7-292038 JP-A-8-53514 U.S. Pat. No. 4,568,732 JP 2001-55407 A JP 2001-55408 A Unexamined-Japanese-Patent No. 2001-55415 JP-A-6-298843 JP, 2008-001771, A JP, 2010-241908, A JP 2012-172112 A JP, 2014-51619, A

  An object of the present invention is to provide a manufacturing method capable of continuously obtaining a living polymer having a low degree of dispersion, in view of the above-mentioned current situation. In addition, the object of the present invention is to industrially operate by using a compact facility capable of effectively controlling the internal temperature of the polymerization vessel and operating the polymerization temperature and the catalyst concentration, and the polymer concentration in the polymerization solution within a specific range. It is also intended to provide a continuous process for the preparation of living polymers useful for Furthermore, an object of the present invention is to provide a continuous production method capable of obtaining a living polymer in which the functional group is introduced to the terminal and the synthesis of the block copolymer is as originally designed.

In the present invention, a solution (A) containing a polymerization initiator, a 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. And the temperature of the temperature control medium supplied to the reactor in the production method for continuously performing living cationic polymerization of the polymerizable monomer by supplying the first reaction portion connected to the subsequent mixing portion. The cross-sectional area of the reaction part is 1 to 400 mm ² , the Lewis acid catalyst concentration in the reaction liquid is 50 to 250 mol / m ³ , and the weight in the polymerization solution obtained at the outlet of the reactor The present invention relates to a method for producing a polymer, which is characterized in that the sum of the concentration of combined and polymerizable monomer is in the range of 15 to 50%.

  Preferably, the present invention relates to a method for producing a polymer, wherein the polymerizable monomer is isobutylene.

  Preferably, the present invention relates to a method for producing a polymer characterized in that an electron donor is contained in a reaction solution.

  Preferably, the present invention relates to a method for producing a polymer, wherein the electron donor is present in a molar ratio of 0.2 to 10 times that of the polymerization initiator.

  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 method for producing a 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 a polymer, wherein the Lewis acid catalyst concentration is 80 to 160 mol / m ³ .

  The present invention also relates to a method for producing a polymer, wherein the polymer is a block copolymer.

  Preferably, the present invention relates to a method for producing a polymer, characterized in that the block copolymer comprises a block mainly containing isobutylene and a block mainly containing an aromatic vinyl monomer.

  The present invention also relates to a method for producing a polymer, which comprises reacting a functional group-introduced substance after completion of polymerization.

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

  According to the continuous production method of the present invention, the residence time can be made constant (the residence time distribution can be narrowed), and the side reaction can be controlled, so that the degree of dispersion of the obtained isobutylene polymer is small. Is effective. Moreover, since it is a continuous polymerization method under high temperature conditions and at a low catalyst concentration and a high polymer concentration in the obtained polymerization solution as compared with the conventional method, industrial economic efficiency is excellent.

Example of continuous production apparatus for isobutylene polymer used in the present invention (schematic diagram) Example of continuous production apparatus of isobutylene-based block copolymer used in the present invention (schematic diagram) Example of continuous production apparatus of isobutylene-based block copolymer introduced functional group used in the present invention (schematic diagram)

(Applicable reaction system)
The production method of the present invention is suitable for living polymerization reaction and is further effective for living cationic polymerization. The details of the living cationic polymerization will be described below. As the living cationic polymerization, for example, the synthesis described in the book of JP Kennedy et al. (Carbocationic Polymerization, John Wiley & Sons, 1982) and the book of 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 polymerizable monomer, and a polymerization solvent, and a solution (B) containing a Lewis acid catalyst and a polymerization solvent are continuously provided. In the production method of continuously performing living cationic polymerization of a polymerizable monomer by supplying to a mixing unit and supplying to a reaction unit connected to the subsequent mixing unit, the temperature of the temperature control medium supplied to the reactor is The cross-sectional area of the reaction part is 1 to 400 mm ² , the Lewis acid catalyst concentration in the reaction solution is 50 to 250 mol / m ³ , in the polymerization solution obtained at the outlet of the reactor The sum of the concentration of the polymer and the polymerizable monomer is in the range of 15 to 50%.

Industrially, a polymer having a molecular weight of several thousand to several tens of thousands is useful for an isobutylene polymer, but a reaction liquid containing a polymer having such a molecular weight has a high viscosity. Therefore, when the cross-sectional area of the reaction part is less than 1 mm ² when flowing the reaction part, restrictions such as a special pump which can send liquid may occur, or clogging of the reaction part may occur due to high viscosity. And other problems arise, so only low molecular weight polymers can be polymerized. Therefore, by setting the cross-sectional area of the reaction part to 1 mm ² or more, it becomes possible to obtain a polymer having a molecular weight of several thousands to several tens of thousands. However, since the heat removal performance heat transfer area per volume of the reaction section to the cross-sectional area of the reaction section is increased becomes smaller drops, the cross-sectional area of the reaction part is 1~400mm ^2.

  In order to allow the reaction to proceed at a low temperature as in the conventional method, a large-scale heat removal facility is required, and a reaction at a high temperature is preferable because a low temperature generally has a high running cost. On the other hand, since the side reaction can not be suppressed if the reaction temperature becomes too high, the temperature of the temperature control medium supplied to the reactor is -55 to -30 ° C. In addition, since the viscosity of the reaction solution is also lowered by the increase of the reaction temperature, it is also advantageous in liquid feeding.

The amount of the Lewis acid catalyst used is such that the Lewis acid catalyst concentration in the reaction solution is 50 to 250 mol / m ³ , and preferably 80 to 160 mol / m ³ . When the amount of the Lewis acid catalyst is too small, the polymerization reaction rate is remarkably suppressed, the cationic polymerization reaction takes a long time, and the productivity is lowered. On the other hand, too much Lewis acid catalyst tends to increase side reactions, and proton initiation reaction and chain transfer reaction occur to increase the degree of dispersion. In addition, polymerization at high catalyst concentration is disadvantageous in industrial production because it increases raw material costs.

  Since the polymer contained in the polymerization solution needs to be separated from the polymerization solvent, the concentration is 15% or more from the viewpoint of productivity. On the other hand, when the concentration of the polymer is too high, there is a restriction that the pump that can send the solution is special when the concentration of the polymer solution is too high, or the reaction part is clogged due to high viscosity. Because it occurs, it is 50% or less. Therefore, the sum of the concentration of the polymer and the polymerizable monomer in the polymerization solution obtained at the outlet of the reactor is in the range of 15 to 50%.

  In the method of the present invention, the polymerization solution having passed through the first reaction section described above and the second polymerizable monomer are continuously supplied to the second mixing section, and the second polymerization section is subsequently connected to the mixing section. The second polymerizable monomer can be polymerized by being supplied to the reaction section of the above to obtain an isobutylene block copolymer. When the second polymerizable monomer is mixed, it is preferable that the first polymerizable monomer is substantially consumed.

  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 a cooling bath, A jacket structure may be provided in the mixing unit and the reaction unit, and heat may be exchanged by passing a refrigerant through the jacket. In addition, the configuration of the cross-sectional area of the mixing unit and the reaction unit, the channel length, the configuration of the material, and the like are not particularly limited and can be appropriately selected according to the reaction. The material can be appropriately selected according to the requirements such as heat resistance, pressure resistance, solvent resistance, processability, etc. For example, stainless steel, titanium, copper, nickel, aluminum, silicon, and Teflon ( (Registered trademark), fluorine resin such as PFA (perfluoro alkoxy resin), TFAA (trifluoroacetamide) and the like.

  The resulting polymerization solution deactivates the catalyst contained in water, alcohols and the like, for example, separates the two phases, and if necessary, the organic phase is washed with water and the organic solvent is distilled off. You can get a union.

(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 are not exhibited, and therefore, it is industrially useful. In view of such materials, it is usually 5,000 to 500,000, more preferably 10,000 to 300,000.

(Polymerization initiator used)
As a method for efficiently performing the initiation reaction of living cationic polymerization, an inifer method has been developed which uses a compound having a chlorine atom bonded to a tertiary carbon or a chlorine compound having an aromatic ring at the α position as a polymerization initiator. This method can be applied to the present invention (US Pat. No. 4,276,394). Any polymerization initiator may be used as the polymerization initiator used in the inifer method, as long as it exhibits its function. As a representative example, one having the following structure can be shown.

(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 each represent a monovalent hydrocarbon group having 1 to 20 carbon atoms. R ³ represents an n-valent carbon atom having 1 to 20 carbon atoms. Represents a hydrocarbon group of n is an integer of 1 to 4)
As a 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 preferred. Bifunctional initiators, such as p-DCC, can be selected when a bifunctional polymer is required. In addition, monofunctional or trifunctional or multifunctional initiators such as TCC can be used as needed. The molecular weight of the polymer can be freely set in accordance with the feed ratio of the polymerization initiator to the monomer.

(Lewis acid catalyst)
The catalyst used for the living cationic polymerization is a Lewis acid catalyst, and specific examples thereof include TiCl ₄ , AlCl ₃ , BCl ₃ , ZnCl ₂ , SnCl ₄ , ethylaluminum chloride, SnBr _{4 and the} like.

(Electron donor)
When using the above-described inifer method, it is effective to use an electron donor to suppress side reactions such as chain transfer reaction and proton initiation reaction to obtain a good polymer (Japanese Patent Laid-Open No. 2-245004). Publication No. 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 (picoline or α-picoline), trimethylamine, dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), ethyl acetate (EtOAc), Ti (OiPr) _{4 and the} like It is preferably used.

  The electron donor is preferably present in the reaction part in a molar ratio of 0.2 to 10 times that of the polymerization initiator. If the amount of the electron donor is too small, side reactions tend to be large, and the degree of dispersion becomes large due to the occurrence of proton initiation reaction or chain transfer reaction. On the other hand, when the amount of the electron donor is too large, the polymerization reaction rate is remarkably suppressed, and the cationic polymerization reaction takes a long time, which lowers the productivity.

(Polymerizable monomer)
The polymerizable monomer component used in the present invention may be any one as long as a polymer can be obtained by using a polymerization initiator and a Lewis acid catalyst.

  When an isobutylene polymer is obtained, the polymerizable monomer component is a monomer mainly containing isobutylene. The term "mainly" refers to one containing 30% or more of isobutylene, preferably 50% or more. It is preferable that isobutylene alone is used from the viewpoint of gas barrier properties and the like.

  When obtaining an isobutylene-based 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 amount The body component is one having a compound and / or composition different from that of the first polymerizable monomer component.

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

  As a polymerizable monomer used for cationic polymerization, olefins having 3 to 12 carbon atoms, conjugated dienes, vinyl ethers, aromatic vinyl compounds and the like can be mentioned. Among these, olefins having 3 to 12 carbon atoms and conjugated dienes are preferred. Specific examples thereof 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 vinyl cyclohexane, butadiene, isoprene, cyclopentadiene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, p-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene and the like. 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-based block copolymer, at least one of the first polymerizable monomer and the second polymerizable monomer is a monomer component mainly containing isobutylene, one of which is mainly aromatic vinyl. It is preferable that it is a monomer component containing a system monomer.

  In the case of an isobutylene polymer, the reaction liquid having passed through the first reaction part and the functional group-introduced substance are continuously supplied to the second mixing part, and the second reaction is subsequently connected to the mixing part. It is possible to obtain an isobutylene-based polymer having a functional group by supplying to a part and reacting a functional group-introduced substance, and in the case of an isobutylene-based block copolymer, a reaction liquid passing through the second reaction part And a functional group-introducing substance are continuously supplied to the third mixing section, and are subsequently supplied to the third reaction section connected to the mixing section to react the functional group-introducing substance, thereby reacting isobutylene type having a functional group A block copolymer may be obtained.

  The functional group introducing substance mentioned here is for introducing a functional group to the obtained polymerization terminal, and it is preferable to use allyltrimethylsilane or diallylsilane from the viewpoint of the reactivity and the utility of the obtained polymer. .

(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 8-53514). As halogenated hydrocarbons, chloroform, methylene chloride, 1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride, n-butyl chloride, 1-chloropropane, 1-chloro-2-methylpropane, 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 and the like can be used, and the solvent selected from these can be used alone. Even if, it may consist of 2 or more types of components.

  As the aliphatic hydrocarbon, butane, pentane, neopentane, n-hexane, heptane, octane, cyclohexane, methylcyclohexane and ethylcyclohexane are preferable, and two or more kinds of solvents may be selected from among these solvents. It may be made of Further, as the aromatic hydrocarbon, benzene, toluene, xylene and ethylbenzene are preferable, and the solvent selected from these solvents may be single or may be composed of two or more kinds of 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 an aliphatic and / or aromatic hydrocarbon is combined with a primary and / or secondary monohalogenated hydrocarbon having 3 to 8 carbon atoms is preferable. Furthermore, it is preferable that it is a mixed solvent of n-butyl chloride and n-hexane.

  Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to only these examples.

The polymer shown in this example was analyzed by the method shown below.
(Analysis of molecular weight and molecular weight distribution)
GPC system manufactured by Waters (column: Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK, mobile phase: chloroform). The molecular weight is expressed in terms of polystyrene.

Example 1
The outline of the device is shown in FIG. Specifically, after preparing 2 pressure-resistant tanks with a volume of 3 L and replacing 2 pressure-resistant tanks and the tubular polymerizer with nitrogen, one tank contains the polymerization solvent (n-butyl chloride, n-hexane in volume) 1293 ml of a 9: 1 ratio), 2.48 g of p-DCC as a polymerization initiator, 1.00 g of 2-methylpyridine as an electron donor, and isobutylene as a first polymerizable monomer 702 ml was charged. In the other pressure-resistant tank, 588 ml of a polymerization solvent (n-butyl chloride and n-hexane mixed at a volume ratio of 9: 1), 27.1 mL of TiCl ₄ as a catalyst, and 2-methylpyridine as an electron donor Was charged 0.132 g. Cooling was performed by immersing two pressure-resistant tanks and a polymerization vessel in a -50 ° C cooling bath. T-shaped mixer with an inner diameter of 2.3 mm in the mixing section of the polymerization vessel, (1) a single tube with an inner diameter of 3 mm and a tube length of 10 m, (2) a single tube with an inner diameter of 4.35 mm and a tube length of 4 m, (3) inner diameter A single tube of 7.53 mm in length and 2 m in length was used. The reaction solution was supplied at a flow rate of 34.5 ml / min and a TiCl ₄ concentration of 105 mol / m ³ . 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) and the degree of dispersion (Mw / Mn) of the obtained polymer were measured by GPC. Table 1 shows the results.

(Example 2)
In one tank, 1138 ml of a polymerization solvent (n-butyl chloride and n-hexane mixed at a volume ratio of 9: 1), 2.48 g of p-DCC as a polymerization initiator, and 2-methyl as an electron donor 1.00 g of pyridine was charged, and 702 ml of isobutylene as a first polymerizable monomer was charged. In the other pressure-resistant tank, 176 ml of a polymerization solvent (n-butyl chloride and n-hexane mixed at a volume ratio of 9: 1), 17.6 ml of TiCl ₄ as a catalyst, and 2-methylpyridine as an electron donor Was charged 0.086 g. The reactor was connected to the reaction part (1) Single tube of inner diameter 3 mm, tube length 10 m, (2) Single tube of inner diameter 4.35 mm, tube length 4 m, (3) Single tube of inner diameter 7.53 mm, tube length 4 m used. The reaction solution was supplied at a flow rate of 30 ml / min and a TiCl ₄ concentration of 104 mol / m ³ . Except for the above, it is the same as Example 1. Table 1 shows the results.

(Example 3)
One tank contains 1452 ml of a polymerization solvent (n-butyl chloride, mixed at a volume ratio of 9: 1 by n-hexane), 1.32 g of p-DCC as a polymerization initiator, and 2-methyl as an electron donor. 2.66 g of pyridine was charged, and 660.6 ml of isobutylene was charged as the first polymerizable monomer. In the other pressure-resistant tank, 211.7 ml of a polymerization solvent (mixture of n-butyl chloride and n-hexane at a volume ratio of 9: 1), 33.9 mL of TiCl ₄ as a catalyst, 2--9 as an electron donor 0.117 g of methylpyridine was charged. The reactor was connected to the reaction part: (1) Single tube with inner diameter 3 mm, tube length 5 m, (2) Single tube with inner diameter 4.35 mm, tube length 4 m, (3) Single tube with inner diameter 7.53 mm, tube length 4 m used. The reaction solution was supplied at a flow rate of 36 ml / min and a TiCl ₄ concentration of 152 mol / m ³ . Except for the above, it is the same as Example 1. Table 1 shows the results.

(Example 4)
One tank contains 1452 ml of a polymerization solvent (n-butyl chloride, mixed at a volume ratio of 9: 1 by n-hexane), 1.00 g of p-DCC as a polymerization initiator, and 2-methyl as an electron donor. 2.02 g of pyridine was charged, and 697.2 ml of isobutylene was charged as a first polymerizable monomer. In the other pressure-resistant tank, 160.4 ml of a polymerization solvent (mixture of n-butyl chloride and n-hexane at a volume ratio of 9: 1), 25.6 ml of TiCl ₄ as a catalyst, and 2- 0.134 g of methylpyridine was charged. The reactor was connected to the reaction part: (1) Single tube with inner diameter 3 mm, tube length 5 m, (2) Single tube with inner diameter 4.35 mm, tube length 4 m, (3) Single tube with inner diameter 7.53 mm, tube length 4 m used. The reaction solution was supplied at a flow rate of 36 ml / min and a TiCl ₄ concentration of 150 mol / m ³ . Except for the above, it is the same as Example 1. Table 1 shows the results.

(Comparative example 1)
In one tank, 1080 ml of a polymerization solvent (n-butyl chloride, mixed at a volume ratio of 9: 1 by n-hexane), 1080 ml, 1.92 g of p-DCC as a polymerization initiator, 2-methyl as an electron donor Pyridine was charged such that the molar ratio to the polymerization initiator in the reaction part was 6, and 470 ml of isobutylene was charged as the first polymerizable monomer. In the other pressure-resistant 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 to the polymerization initiator of 200 after mixing TiCl ₄ as a catalyst It was thrown in to become. A T-shaped mixer with an inner diameter of 1.3 mm was used for the mixing section of the polymerization vessel, and a single pipe with an inner diameter of 3 mm and a pipe length of 10 m was used for the reaction section. It supplied so that the flow rate of the reaction liquid might be 70 ml / min. Except for the above, it is the same as Example 1. Table 1 shows the results.

(Comparative example 2)
In Comparative Example 1, 2-methylpyridine as an electron donor is charged so that the molar ratio to the polymerization initiator in the reaction part is 1, and the molar ratio to the polymerization initiator after mixing TiCl ₄ as a catalyst is 180 It charged so that it might become, and it was made the same except using the single tube of internal diameter 2mm and tube length 10m as a reaction part, and supplying so that the flow volume of the reaction liquid might be 60 ml / min. Table 1 shows the results.

(Comparative example 3)
One tank contains 500 ml of a polymerization solvent (n-butyl chloride, mixed at a volume ratio of 9: 1 by n-hexane), 1.06 g of p-DCC as a polymerization initiator, and 2-methyl as an electron donor. 0.43 g of pyridine was charged, and 300.4 ml of isobutylene as a first polymerizable monomer was charged. In the other pressure-resistant tank, 233.3 ml of a polymerization solvent (mixture of n-butyl chloride and n-hexane at a volume ratio of 9: 1), 30.2 ml of TiCl ₄ as a catalyst, and 2-0.2 as an electron donor 0.052 g of methylpyridine was charged. A single tube with an inner diameter of 3 mm and a tube length of 5 m was used for the reaction part. The reaction solution was supplied at a flow rate of 30 ml / min and a TiCl ₄ concentration of 459 mol / m ³ . Except for the above, it is the same as Example 1. Table 1 shows the results.

(Comparative example 4)
The same as in Comparative Example 3, except that the flow rate of the reaction solution was 51 ml / min and the TiCl ₄ concentration was 267 mol / m ³ . Table 1 shows the results.

(Comparative example 5)
In one tank, 1001 ml of a polymerization solvent (n-butyl chloride, mixed at a volume ratio of 9: 1 by n-hexane), 1.06 g of p-DCC as a polymerization initiator, 2-methyl as an electron donor 0.43 g of pyridine was charged, and 300.4 ml of isobutylene as a first polymerizable monomer was charged. In the other pressure-resistant tank, 466.7 ml of a polymerization solvent (mixture of n-butyl chloride and n-hexane at a volume ratio of 9: 1), 20.1 ml of TiCl ₄ as a catalyst, 2-1-2 as an electron donor 0.104 g of methylpyridine was charged. The reaction solution was supplied at a flow rate of 38 ml / min and a TiCl ₄ concentration of 59.3 mol / m ³ . Except for the above, it is the same as Example 1. Table 1 shows the results.

(Comparative example 6)
The same as in Comparative Example 5, except that the flow rate of the reaction solution was 36 ml / min and the TiCl ₄ concentration was 41.7 mol / m ³ . Table 1 shows the results.

  All of the monomers were consumed in Examples 1 to 4 and Comparative Examples 1 to 4, and a polymer having a narrow molecular weight distribution was obtained, but the molecular weight of Examples 1 to 4 was more than that of Comparative Examples 1 to 4 A narrow polymer was obtained. Further, in Comparative Examples 5 and 6, unreacted monomers remained at the outlet of the reactor, and there was a problem that the reaction was not completed.

As apparent from the above, the Lewis acid catalyst concentration in the reaction solution is 50 to 250 mol / m ³ , and the sum of the concentration of the polymer and the polymerizable monomer in the polymerization solution obtained at the reactor outlet is 15 to 15 By setting the content in the range of 50%, the present invention does not require a large amount of catalyst to complete the polymerization as compared with the conventional method, and further, by suppressing side reactions, the structure of the polymer can be controlled. The method is good.

  An outline of an apparatus used for continuous polymerization of a block copolymer is shown in FIG.

(Example 5)
Specifically, a static mixer (inner diameter 5 mm, pipe length 165 mm, 21 elements, manufactured by Noritake Kanpani (type: T4-21)) is used for the second mixing unit, and an inner diameter is 7.53 mm for the second reaction unit. A single pipe of 4 m in length was used. The second pressure-resistant tank for polymerizable monomer is replaced with nitrogen to charge the polymerization solvent (mixture of n-butyl chloride and n-hexane at a volume ratio of 9: 1) and styrene at a volume ratio of 1: 1. It is. The polymerization of the first polymerizable monomer is carried out under the same conditions as in Example 4, and subsequently, styrene is used as the second polymerizable monomer in the second mixed portion, relative to the first polymerizable monomer. It supplied so that it might be set to 0.114 by molar ratio. Table 2 shows the results.

  As apparent from Example 5, the continuous production method according to the present invention can obtain a block copolymer with a narrow molecular weight distribution by an industrially economical procedure.

1. First pressure-resistant tank for polymerizable monomer Catalyst pressure tank 3. Transfer pump 4. First mixing unit 5. First reaction part 6. Second pressure-resistant tank for polymerizable monomer Second mixing unit 8. Second reaction part 9. Pressure-resistant tank for functional group introduced substance 10. Third mixing unit 11. Third reaction part

Claims (10)

A solution (A) containing a polymerization initiator, a 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, and In the production method in which living cationic polymerization of the polymerizable monomer is continuously performed by supplying the first reaction portion connected to the mixing portion, the temperature of the temperature control medium supplied to the reaction device is -55 to -30. The cross-sectional area of the reaction part is 1 to 400 mm ² , the Lewis acid catalyst concentration in the reaction solution is 104 to 250 mol / m ³ , and the polymer and polymerizability in the polymerization solution obtained at the outlet of the reactor A method of producing a polymer, wherein the sum of the concentration of monomers is in the range of 15 to 50%.   The method for producing a polymer according to claim 1, wherein the polymerizable monomer is isobutylene.   An electron donor is contained in a reaction liquid, The manufacturing method of the polymer of Claim 1 or 2 characterized by the above-mentioned.   The method for producing a polymer according to claim 3, wherein the electron donor is present in a molar ratio of 0.2 to 10 times the amount of the polymerization initiator.   The polymerization initiators are (1-chloro-1-methylethyl) benzene, 1,4-bis (1-chloro-1-methylethyl) benzene, and 1,3,5-tris (1-chloro-1-methyl) It is an at least 1 sort (s) of compound selected from the group which consists of ethyl) benzene, The manufacturing method of the polymer in any one of the Claims 1-4 characterized by the above-mentioned. Method for producing a polymer according to claim 1, the Lewis acid catalyst concentration is characterized by a 104 ~160mol / ^{m 3.}   The method of producing a polymer according to any one of claims 1 to 6, wherein the polymer is a block copolymer. The method for producing a polymer according to claim 7, wherein the block copolymer comprises a block mainly containing isobutylene and a block mainly containing an aromatic vinyl monomer.   The method for producing a polymer according to any one of claims 1 to 8, wherein a substance introducing a functional group is reacted after completion of the polymerization. 10. The method for producing a polymer according to claim 9, wherein the functional group introducing substance is allyltrimethylsilane or diallylsilane.

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