JP2003292504A - Method for producing isobutylene-based polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing an isobutylene-based polymer and its derivative having a low degree of dispersion and desired molecular structure by controlling a reaction rate and suppressing abrupt heat generation. <P>SOLUTION: The method for producing the isobutylene-based polymer comprises adding a polymerization catalyst and an electron donor dividedly one after another, respectively to a solution containing an isobutylene monomer and a polymerization initiator. The method for producing the isobutylene-based block copolymer comprises reacting the isobutylene-based polymer with a cationic polymerizable monomer different from isobutylene. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an isobutylene polymer and an isobutylene block copolymer. More specifically, the present invention relates to a production method for controlling a reaction rate during polymerization to suppress abrupt heat generation.

[0002]

2. Description of the Related Art Isobutylene polymers are liquid rubbers having excellent viscoelasticity, weather resistance and gas permeation barrier properties. When the isobutylene-based polymer is cross-linked, it becomes a rubber-like cured product, which is used as a coating material, a sealing material for construction, a sealing material for electronic materials and the like.

Further, when an isobutylene polymer is block-copolymerized with, for example, an aromatic vinyl compound, it becomes a rubber-like elastomer at room temperature and becomes a thermoplastic elastomer which flows when heated and can be processed and molded. This isobutylene-based copolymer can have high functionality such as heat resistance, weather resistance, vibration control, and gas barrier property. Utilizing this property, it is used for applications such as fire-resistant foam sheets, vibration control materials, and tire modifiers.

The narrower the molecular weight distribution of these isobutylene-based polymers, the lower the viscosity, and thus the workability is improved.
When introducing a functional group for a cross-linking reaction, it is necessary to introduce the functional group into all polymers as much as possible in a designed ratio. Further, when block-copolymerizing an isobutylene-based polymer and a monomer other than isobutylene,
It is desirable to control so that all the polymers are copolymerized as much as possible. The living polymerization technique is effective for efficiently obtaining an isobutylene polymer satisfying these requirements.

Living polymerization is polymerization in which a molecular chain grows without being hindered by a side reaction such as a termination reaction or a chain transfer reaction in a polymerization reaction starting from an initiator.
Therefore, in living polymerization, a polymer having a uniform molecular weight can be obtained if the polymerization reactions start at the same time. Furthermore, since the terminal of the polymer remains active, it is possible to synthesize a copolymer by introducing a specific functional group or adding a different type of monomer. Living cationic polymerization (for example, JP-A-7-29) depending on the type of monomer to be polymerized.
2038, JP-A-8-53514), living anionic polymerization (for example, JP-A-5-247199), or living radical polymerization (for example, JP-A-10-30610).
6) etc.

Isobutylene is a typical cationically polymerizable monomer, and the production of polyisobutylene using the technique of living cationic polymerization is carried out on an industrial scale. In the living cationic polymerization, a polymerization initiator and a polymerization catalyst are used in addition to the cationically polymerizable monomer, and an electron donor is added for the purpose of stabilizing the polymerization reaction.

The growth terminal of living cationic polymerization does not always have to be a carbocation, and the carbocation may be bound to a counter anion during the polymerization reaction to be in a nonionic state. Living cationic polymerization systems often maintain an equilibrium between ionic (i.e. carbocation) and non-ionic ends, in which case the active carbocation end reacts with the monomer. That is, strictly speaking, living cationic polymerization includes those classified as pseudo-living polymerization. Such living cationic polymerization is often carried out at an extremely low temperature, and the catalysts and additives have been devised unique to each polymerization system. Regarding the cationic polymerization of isobutylene, for example, in Japanese Patent Application Laid-Open No. 7-292038 (Noda et al.), The result of evaluating the dispersity (Mw / Mn), which is the ratio of the weight-based average molecular weight (Mw) and the number-based average molecular weight (Mn), is shown. 1.09 ~
It is 1.38, and the polydispersity is similarly 1.07 to 1.33 in JP-A-8-53514 (Maeda et al.), And a polymer having a uniform molecular weight is obtained in these systems.

In the conventional living cationic polymerization reaction, all the reaction raw materials were charged in a stirred tank type reactor to start the polymerization, that is, batchwise polymerization. However, in the conventional batch polymerization method, a rapid reaction heat is generated immediately after the start of the polymerization reaction, and the temperature inside the reactor rises. If it is a relatively small reactor, heat removal is easy if a reactor with a jacket is used, but if the reactor is enlarged to produce on an industrial scale, the heat transfer area per reaction liquid is small. Therefore, heat removal becomes difficult. Since the carbocation is less stable as the temperature is higher, if the heat is not sufficiently removed and the temperature rises, side reactions such as a chain transfer reaction and a polymerization termination reaction easily proceed. When these side reactions occur,
Even if an attempt is made to introduce a functional group to the polymer terminal, the functionalization rate becomes insufficient, or even if a block copolymer is synthesized, a polymer consisting of a single component is mixed, and the target product is obtained. There is no problem.

For these reasons, it is necessary to remove heat particularly immediately after the start of the polymerization reaction. To improve the efficiency of reaction heat removal, install a reflux condenser,
Large-scale equipment is required, such as installing a cooling coil inside the reactor and circulating a large amount of brine using a large refrigerator. Further, if a method such as lowering the polymerization reaction rate or lowering the concentration of the polymerizable monomer is applied, the rapid reaction is suppressed, but on the other hand, the productivity is greatly reduced. These are problems peculiar to batch operation.

A so-called continuous polymerization method, in which the raw materials are continuously supplied to the reactor and the reaction solution is continuously discharged, has been proposed as a method for suppressing a rapid temperature rise, which is a problem of the batch polymerization method. ing. In the continuous polymerization system, one or more flow type stirred tank reactors are connected in series, or a flow pipe reactor is used (for example, US Pat. −
298843). However, there is a concern that the degree of dispersion of the obtained polymer becomes large due to the spread of the residence time distribution of the reaction liquid. For example, in a liquid polymer product, even if the average molecular weight is the same, the viscosity varies depending on the value of dispersity. The same number average molecular weight (Mn) and dispersity (M
The difference of w / Mn means that the weight average molecular weight (Mw) is different after all. Since the viscosity of the polymer is determined by the value of Mw, the Mw
Often becomes large and the viscosity of the polymer becomes high, which makes it difficult to handle the product. Another problem is that the continuous polymerization method is suitable for large-scale production of a single product, and when trying to manufacture multiple products, it is necessary to repeatedly shut down and start up frequently. Causes a large amount of product loss. These are important issues specific to continuous operation.

As an effective polymerization system other than the batch system and the continuous system, a part of the raw materials used for the polymerization are fed to the stirred tank type reactor in batches, and the other raw materials are fed continuously or in a divided manner. The palindrome method can be mentioned. JP-A-8
No. 337615 shows a method for producing an isobutylene-based polymer having a narrow molecular weight distribution by adding a catalyst in a divided manner. However, if the catalyst is simply added in portions, the initiation reaction will be relatively slower than in the case where it is added all at once, so the molecular weight distribution becomes wider and polymerization from the initiation point preferentially proceeds from other than the initiator. However, there is a problem that the reaction is not sufficiently controlled.

[0012]

An object of the present invention is to efficiently control an isobutylene polymer and its derivative having a desired molecular structure with a small degree of dispersion by controlling the reaction rate and suppressing abrupt heat generation. It is to provide a method of manufacturing well.

[0013]

[Means for Solving the Problems] The present inventors diligently studied a method for controlling the molecular structure of an isobutylene polymer and its derivative using the living cationic polymerization method. As a result, the important factor that determines the molecular structure is the reaction temperature,
It was found that controlling the addition method of the polymerization catalyst and the electron donor is an effective method for controlling the reaction temperature. That is, the present invention is a method for producing an isobutylene-based polymer, characterized in that a solution containing an isobutylene monomer and a polymerization initiator are separately added in sequence to a polymerization catalyst and an electron donor, and the above-mentioned division is performed. It is preferable that the polymerization catalyst and the electron donor are divided and added successively in a range of 2 to 5 times.

The polymerization initiator is (1-chloro-1
-Methylethyl) benzene, 1,4-bis (1-chloro-1-methylethyl) benzene, 1,3,5-tris (1-chloro-1-methylethyl) benzene Is preferred, and the polymerization catalyst is preferably TiCl ₄ . The electron donor is preferably at least one substance selected from pyridine, 2-methylpyridine, trimethylamine, dimethylacetamide, dimethylsulfoxide, ethyl acetate and titanium tetraisopropoxide.

On the other hand, as another method of the present invention, a cationically polymerizable monomer different from isobutylene is added to the liquid containing the isobutylene polymer obtained above to react with the isobutylene polymer. In the method for producing a characteristic isobutylene-based block copolymer, it is preferable that the cationically polymerizable monomer different from isobutylene is an aromatic vinyl compound.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
For details of living cationic polymerization to which the present invention can be applied, see, for example, JP Kennedy et al.
(Polymerization Polymerization, John Wiley & Sons, 1982)
And K. Matyjaszewski et al. (Cationic Polymerization
S., Marcel Dekker, 1996) for a summary of synthetic reactions.

(Polymerizable Monomer) As the cationic polymerizable monomer used in the living cationic polymerization of the present invention,
In addition to isobutylene, olefins having 3 to 12 carbon atoms,
Examples thereof include conjugated dienes, vinyl ethers and aromatic vinyl compounds. Specific examples include propylene, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-2-butene, pentene, 4-methyl-1-pentene,
Hexene, 5-ethylidene norbornene, vinyl cyclohexane, butadiene, isoprene, cyclopentadiene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, p-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene , Inden, etc. Among these, isobutylene, propylene, 1-butene, 2-butene, styrene, p-methylstyrene, α-methylstyrene, indene, β-pinene, isoprene, cyclopentadiene and the like are preferable.

(Polymerization Initiator) As a method for efficiently carrying out the initiation reaction of living cationic polymerization, a compound having a chlorine atom bonded to a tertiary carbon or a compound such as a chlorine compound having an aromatic ring at the α-position is used as a polymerization initiator. The inifer method used as the above has been developed (US Pat. No. 4,276,394), and this method can be applied to the present invention. The polymerization initiator used in the inifer method may be any one that exhibits its function, and representative examples thereof include those having the following structures.

(X-CR ¹ R ² ) _n R ³ [wherein, X represents a halogen atom, R ¹ and R ² are the same or different and each represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. . R ³ represents an n-valent hydrocarbon group having 1 to 20 carbon atoms.
n is an integer of 1 to 4].

The type of initiator that can be used in the present invention is described in JP-A-7-292038 (Noda et al.), But as a preferable polymerization initiator from the viewpoint of the stability of the terminal cation, (1-chloro) is used. -1-Methylethyl) benzene (also called cumyl chloride), 1,4-bis (1-chloro-1-methylethyl) benzene (p-DC
C or dicumyl chloride), 1,3,5-tris (1-chloro-1-methylethyl) benzene (TC
Substances containing an aromatic ring such as C or tricumyl chloride) and their derivatives can be used, and these can be used alone or as a mixture. These initiators have one or more polymerization initiation points, but since the number of polymerization initiation points of the initiator is reflected in the primary structure of the obtained polymer, the initiator should be selected according to the desired polymer. good. A bifunctional initiator such as p-DCC can be selected when a bifunctional polymer is required. In addition, a monofunctional initiator, a trifunctional initiator such as TCC, or a polyfunctional initiator can be used as necessary. In order to set the molecular weight of the polymer, the ratio of the weight of the monomer, which is approximately the molecular weight of the polymer to be synthesized, may be set to 1 mole of the polymerization initiator. For example, when 10000 g of a monomer is added to 1 mol of an initiator, the polymer can have a molecular weight of about 10,000. 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, and more preferably 300 from the viewpoint of easy-to-handle viscosity and solubility in a polymerization solvent.
It is 0-200000.

(Polymerization Catalyst) A Lewis acid catalyst is used in the living cationic polymerization of the present invention. As a specific example, T
iCl ₄ , AlCl ₃ , BCl ₃ , ZnCl ₂ , SnC
l ₄ , ethyl aluminum chloride, SnBr _{4 and the} like. Among these, TiCl ₄ is particularly preferable in terms of easiness of handling, high polymerization activity, economical efficiency and the like.

The total amount of the Lewis acid catalyst used may be determined based on the amount of isobutylene monomer from the viewpoint of the growth reaction, and may be determined based on the initiator from the viewpoint of the initiation reaction. Specifically, when the total addition amount of the Lewis acid catalyst is determined based on isobutylene, 0.0001 to 10 based on the isobutylene monomer amount is used.
The number of moles is preferably double, and more preferably 0.001 to 1 time. This range is preferable because it is easy to control the growth reaction. When the total amount of the Lewis acid catalyst added is determined based on the amount of the initiator, the number of moles is preferably 0.1 to 1000 times the amount of the initiator, and is 0.5 to 500. More preferably, the number of moles is doubled. This range is preferred because it is easy to control the initiation reaction.

In the present invention, the above-mentioned polymerization catalyst is divided and added successively to initiate the polymerization, and the polymerization rate is controlled. The method of the present invention can suppress a rapid temperature rise as compared with the batch system in which the catalyst is added in the total amount all at once, and the side reaction can be suppressed by making the reaction conditions during the initiation reaction mild. If the amount of the catalyst added when starting the polymerization is extremely small, the initiation reaction rate will be significantly slowed down. Therefore, the amount of the catalyst added when starting the polymerization is more preferably half or more of the total amount of the catalyst. Furthermore, the remaining catalyst is later divided and added successively to accelerate the reaction rate and promote the polymerization.
In the sequential addition of the catalyst, the number of divisions is not particularly limited, but if the number of divisions is too large, the operation itself becomes complicated, but the effect itself obtained by the present invention does not change, which is convenient. Considering comprehensively
It is preferable to divide into 5 times and add them sequentially. When the heat generated by the reaction is very small or the reaction time is very short, the number of divisions should be about twice. When the heat generated by the reaction is very large or the reaction time is very long, the number of divisions should be increased more than three times. In addition to these, when the heat generated by the reaction or the reaction time is at a general level, the number of divisions is preferably about 3 times. There is no particular limitation on the amount of catalyst to be added after the second time. However, since the reaction rate significantly decreases as the reaction progresses, the third time and the third time than the second time
It is preferable to divide the catalyst so that the amount of catalyst added in the fourth time is larger than that in the fourth time. The timing of addition is not particularly limited, but it is preferable to add when the reaction rate has decreased, that is, when the temperature of the reaction solution once rises by adding a catalyst and then starts to decrease again. It is preferable to add the second and subsequent additions after 1/3 or more of the polymerization time has elapsed. In addition, the flow rate of addition when continuously adding the catalyst is not particularly limited.

(Electron Donor) When performing living cationic polymerization, an electron donor is used as an additional measure for suppressing side reactions such as chain transfer reaction and proton initiation reaction to obtain a good polymer. It has been reported (JP-A-2-245004, JP-A-1-318014, JP-A-3-174403). In the present invention, it is necessary to use an electron donor. Examples of the electron donor used include pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom. Specific examples include pyridine, 2-methylpyridine (abbreviated as picoline or α-picoline), trimethylamine, dimethylacetamide,
It is preferable to use dimethyl sulfoxide, ethyl acetate, titanium tetraisopropoxide, or the like, and 2-methylpyridine or dimethylacetamide is particularly preferable from the viewpoint of easy handling and economical efficiency.

Since the electron donor is added to control the activity of the catalyst and keep the stability of the reaction, the addition amount of the electron donor is based on the amount of the polymerization catalyst present in the reaction solution. good. The addition amount of the electron donor in the present invention is controlled so that the amount of the electron donor present in the reaction solution is 0.01 to 1 times the amount of the polymerization catalyst present in the reaction solution. Is preferable, and 0.02 to 0.
It is more preferable to control the amount to be 5 times. If the amount of the electron donor is too small, side reactions tend to increase, and side reactions such as a proton initiation reaction and a chain transfer reaction occur to increase the degree of dispersion and to introduce a functional group into the polymer terminal. Problems such as not working as designed occur. On the other hand, if the amount of the electron donor is too large, the cationic polymerization reaction will be remarkably slowed and the productivity will be reduced. Therefore, in the present invention in which the catalyst is divided and sequentially added, it is necessary to operate so that the ratio of the electron donor to the catalyst in the reaction liquid is within the above range by also dividing and sequentially adding the electron donor. .

(Reaction temperature) The reaction temperature of the living cationic polymerization of the present invention is preferably in the range of -90 to -30 ° C. Under relatively high temperature conditions, the reaction rate is slow and side reactions such as chain transfer reactions occur, so it is more preferable to keep the temperature lower than -30 ° C. But the reaction temperature is
If the temperature is lower than 90 ° C, a substance (raw material or polymer) involved in the reaction may be precipitated.

(Reaction Solvent) In the living cationic polymerization of the present invention, a reaction solvent is used, and a single solvent selected from the group consisting of halogenated hydrocarbons, aliphatic hydrocarbons and aromatic hydrocarbons, or a mixed solvent thereof is used. (Japanese Patent Laid-Open No. 8-53514).

As the halogenated hydrocarbon, 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-chloroheptane, 1-chlorooctane, 2-chloropropane, 2-chlorobutane, 2-
Chloropentane, 2-chlorohexane, 2-chloroheptane, 2-chlorooctane, chlorobenzene and the like can be used. Even if the solvent selected from these is 2
It may consist of one or more components.

As the aliphatic hydrocarbon, butane, pentane, neopentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and ethylcyclohexane are preferable, and the solvent selected from these may be a single solvent or two or more kinds. It may consist of components.

As the aromatic hydrocarbon, benzene,
Toluene, xylene and ethylbenzene are preferable, and the solvent selected from these may be a single solvent or a solvent composed of two or more components.

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

For example, when n-butyl chloride and an aliphatic hydrocarbon are mixed to prepare a solvent, n-butyl chloride in the mixed solvent is used.
The content of butyl chloride is not particularly limited, but can be generally in the range of 10 to 100% by weight, more preferably 50 to 100% by weight.

When a reaction solvent is used as an embodiment of the present invention, the concentration of the polymer is 5 to 80% by weight in consideration of the solubility of the obtained polymer, the viscosity of the solution and the ease of heat removal. It is preferable to use such a solvent, and it is more preferable to use 10 to 60% by weight from the viewpoint of production efficiency and operability.

(Impurities) Various raw materials used in the present invention include:
It is possible to use industrially or experimentally available ones, but the raw materials include substances with active hydrogen such as water, alcohol, hydrochloric acid, and compounds with chlorine atoms bonded to tertiary carbon other than the initiator. If they are contained, they will cause side reactions as impurities, so it is necessary to purify them to a concentration as low as possible beforehand. Further, it is necessary to prevent these impurities from entering from the outside during the reaction operation. In order to efficiently obtain the target polymer, it is preferable to suppress the total number of moles of impurities to 1 time or less, more preferably 0.5 times or less, based on the total number of polymerization initiation points of the initiator. preferable.

(Operation of Reactor) The greatest feature of the present invention is that, at the start of polymerization, the entire amount of the polymerization catalyst and the electron donor used in the reaction are not put in the reactor, and the electron donor is sequentially added together with the polymerization catalyst during the polymerization. Alternatively, it is to add continuously. If all of the catalyst required for polymerization is added at the beginning of the reaction at the same time, the concentration of the catalyst will become too high and the temperature will rise rapidly, and side reactions will be likely to occur. It is effective to suppress the temperature rise of. Generally, the reaction temperature of living cationic polymerization is carried out in the range of −90 to −30 ° C., and a refrigerator for removing heat in this low temperature region is often expensive,
From the viewpoint of reducing the cost of the refrigerator process in the manufacturing facility, suppressing the temperature rise is extremely effective.

On the other hand, when only a small amount of catalyst is added at the start of the reaction, the polymerization reaction rate becomes slow when the reaction proceeds and the concentration of the polymerizable monomer decreases. Therefore, the operation of adding the catalyst sequentially or continuously after the start of the polymerization is extremely effective because the reaction rate can be accelerated and the polymerization time can be shortened while suppressing the temperature rise and side reactions.

When the catalyst and the electron donor are mixed for a long time, they may chemically change, so it is preferable to add them separately and mix them in the reactor. The catalyst and the electron donor can be diluted with any solvent and added to the reactor. It is preferable to use a polymerization solvent as the solvent species to be diluted. Some catalysts and electron donors have a relatively high freezing point.Be sure to dilute them with a solvent beforehand to prevent them from solidifying at the moment they are added to the reactor and not being uniformly dispersed in the reaction solution. Is valid.
Further, since the amounts of the catalyst and the electron donor used are generally small and it is relatively difficult to control the amount added, it is effective to enhance the quantitativeness of the amount added by diluting with a solvent.

(Reactor) In the present invention, the form of the reactor is not particularly limited, but a stirred tank reactor is preferred. The structure thereof is not particularly limited, but has, for example, a structure capable of cooling at a jacket portion, a polymerization initiator charged in a reactor, a monomer and a catalyst sequentially supplied, and an electron donor. It is preferable that the structure is such that the can be uniformly mixed and reacted. The structure may be such that an auxiliary facility such as an internal cooling coil or a reflux condenser is provided to improve the cooling capacity, or a baffle plate is provided to improve the mixing state. The stirring blade used in the stirring tank reactor is not particularly limited, but it is preferable that the reaction solution circulates vertically and the mixing performance is high, and the polymerization / reaction solution viscosity is comparatively several centipoise. In a low-viscosity region, a (multi-stage) inclined paddle blade, a stirring blade such as a turbine blade, in a medium-viscosity region of several tens of centipoise to several hundred poises, a Maxblend blade, a full-zone blade, a sun melon blade, a Hi-F mixer blade, and Japanese Patent Laid-Open No. Hei 10 A large blade having a large bottom paddle such as the one described in -24230, and an anchor blade, a (double) helical ribbon blade, and a log bone blade are preferably used in a high viscosity region of several hundred poises or more.

(Preferred embodiment of the present invention) As a preferred method of the present invention, a polymerization catalyst and an electron donor are separately added to a solution containing an isobutylene monomer and a polymerization initiator in a divided manner. In the above-mentioned division, it is preferable to add the polymerization catalyst and the electron donor in a range of 2 to 5 times and add them sequentially.

As the monomer, only one kind of isobutylene may be used alone, or a monomer other than isobutylene may be used together with isobutylene. That is, if a cationically polymerizable monomer other than isobutylene is charged in advance in a reactor together with isobutylene and the above operation is performed, it is possible to obtain a product in which isobutylene and a cationically polymerizable monomer other than isobutylene are randomly copolymerized.

The polymerization initiator is (1-chloro-1
-Methylethyl) benzene, 1,4-bis (1-chloro-1-methylethyl) benzene, 1,3,5-tris (1-chloro-1-methylethyl) benzene Is preferred, and the polymerization catalyst is preferably TiCl ₄ . The electron donor is preferably at least one substance selected from pyridine, 2-methylpyridine, trimethylamine, dimethylacetamide, dimethylsulfoxide, ethyl acetate and titanium tetraisopropoxide.

Further, it is possible to block-copolymerize the isobutylene polymer obtained by the method of the present invention by subsequently reacting a cationically polymerizable monomer other than isobutylene. When producing a block copolymer,
It is preferable to have a block containing an aromatic vinyl compound as a main component (that is, a block containing 50% by weight or more of an aromatic vinyl compound), and it is more preferable that the aromatic vinyl compound is styrene.

[0043]

EXAMPLES Specific examples of the present invention will be described below. Various measurement and analysis methods were performed as follows.

(Peak Molecular Weight (Mp) and Dispersion (Mw / Mn) of Molecular Weight Distribution of Isobutylene Polymer) Determined by gel permeation chromatography (GPC) using a polystyrene gel column having chloroform as a mobile phase.

(Tensile Strength) A 2 mm thick press sheet was punched out into a dumbbell No. 3 type and subjected to a tensile test in accordance with JIS K 6251 to obtain it.

(Temperature increase peak of reaction solution) The temperature of the reaction solution is T
It was measured in real time using a thermocouple of the type. here,
The maximum value of the reaction solution temperature during the polymerization of isobutylene after the initiation of the polymerization was taken as the temperature rising peak of the reaction solution.

(Heat removal load peak) The temperature of brine inlet and outlet was measured in real time using a T-type thermocouple. The heat removal load was calculated from the difference in temperature between the brine jacket reactor and the brine, the specific heat of the brine, and the brine flow rate. Here, the maximum value of the heat removal load during the polymerization of isobutylene after the initiation of the polymerization was taken as the heat removal load peak.

Example 1 In a reaction vessel, 210 ml of butyl chloride as a solvent, 150 ml of hexane, 50 ml of isobutylene as a monomer, and p-D as an initiator were used.
CC 0.18 g, DMAc 0.07 as electron donor
Charge g. A dry ice-ethanol bath is placed around the outer periphery of the reaction vessel and the temperature is brought to -75 ° C while stirring and mixing. The reaction is started by adding 1.3 ml of TiCl ₄ as a catalyst to the reaction vessel. 45 minutes after the start of the reaction, 0.4 ml of TiCl ₄ and 0.02 g of DMAc are added to continue the polymerization reaction. After 70 minutes from the start of the reaction, T
The polymerization reaction is continued by adding 0.7 ml of iCl ₄ and 0.04 g of DMAc. After completion of the reaction (after 120 minutes), the reaction solution was poured into a large amount of water and washed by stirring, and the organic phase and the aqueous phase were separated to remove the catalyst. Further, the volatile components in the organic phase were removed to obtain a polymer product. The experimental results are shown in Table 1.

Comparative Example 1 In a reaction vessel, 210 ml of butyl chloride as a solvent, 150 ml of hexane, 50 ml of isobutylene as a monomer, and p-D as an initiator were used.
CC 0.18 g, DMAc 0.13 as electron donor
Charge g. A dry ice-ethanol bath is placed around the outer periphery of the reaction vessel and the temperature is brought to -75 ° C while stirring and mixing. The reaction is started by adding 2.4 ml of TiCl ₄ as a catalyst to the reaction vessel. After the completion of the reaction (after 90 minutes), the reaction solution was poured into a large amount of water and washed by stirring, and the organic phase and the aqueous phase were separated to remove the catalyst. Further, the volatile components in the organic phase were removed to obtain a polymer product. The experimental results are shown in Table 1.

[0050]

[Table 1] As is clear from Example 1 and Comparative Example 1 described above, the exothermic peak can be suppressed to about 1/2 in the method of the present invention as compared with the conventional method. Further, it can be seen that the degree of dispersion of the product polymer became small and the side reaction could be suppressed.

(Example 2) 210 ml of butyl chloride as a solvent, 150 ml of hexane, 50 ml of isobutylene as a monomer, and p-D as an initiator were placed in a reaction vessel.
CC 0.18 g, DMAc 0.07 as electron donor
Charge g. A dry ice-ethanol bath is placed around the outer periphery of the reaction vessel and the temperature is brought to -75 ° C while stirring and mixing. The reaction is started by adding 1.3 ml of TiCl ₄ as a catalyst to the reaction vessel. 45 minutes after the start of the reaction, 0.4 ml of TiCl ₄ and 0.02 g of DMAc are added to continue the polymerization reaction. After 70 minutes from the start of the reaction, T
The polymerization reaction is continued by adding 0.7 ml of iCl ₄ and 0.04 g of DMAc. After completion of the isobutylene reaction (120
15 minutes later, 15 g of styrene was further added as a monomer to carry out a block copolymerization reaction. After completion of reaction (9
After 0 minutes, the reaction solution was poured into a large amount of water and washed by stirring, and the organic phase and the aqueous phase were separated to remove the catalyst. Further, the volatile components in the organic phase were removed to obtain a polymer product. The results of measuring the tensile strength of the obtained polymer are shown in Table 2.

(Comparative Example 2) 210 ml of butyl chloride as a solvent, 150 ml of hexane, 50 ml of isobutylene as a monomer, and p-D as an initiator were placed in a reaction vessel.
CC 0.18 g, DMAc 0.13 as electron donor
Charge g. A dry ice-ethanol bath is placed around the outer periphery of the reaction vessel and the temperature is brought to -75 ° C while stirring and mixing. The reaction is started by adding 2.4 ml of TiCl ₄ as a catalyst to the reaction vessel. After completion of the isobutylene reaction (after 90 minutes), styrene as a monomer was further added.
A block copolymerization reaction was carried out by adding 5 g. After completion of the reaction (after 90 minutes), the reaction solution was poured into a large amount of water and washed by stirring, and the organic phase and the aqueous phase were separated to remove the catalyst. Further, the volatile components in the organic phase were removed to obtain a polymer product. The results of measuring the tensile strength of the obtained polymer are shown in Table 2.

[0053]

[Table 2] As is clear from Example 2 and Comparative Example 2, the method of the present invention can improve the tensile strength of the product polymer as compared with the conventional method.

Example 3 In a reaction vessel, 340 ml of butyl chloride as a solvent, 240 ml of hexane, 140 ml of isobutylene as a monomer, and p- as an initiator.
DCC 0.29 g, DMAc 0.1 as electron donor
Charge 3g. A dry ice-ethanol bath is placed around the outer periphery of the reaction vessel and the temperature is brought to -75 ° C while stirring and mixing. The reaction is started by adding 2.8 ml of TiCl ₄ as a catalyst to the reaction vessel. 50 minutes after the start of the reaction, 1.1 ml of TiCl ₄ and 0.03 g of DMAc are added to continue the polymerization reaction. 75 minutes after the start of the reaction, T
The polymerization reaction is continued by adding 1.0 ml of iCl ₄ and 0.04 g of DMAc. After completion of the isobutylene reaction (105
15 minutes later, 15 g of styrene was further added as a monomer to carry out a block copolymerization reaction. After completion of reaction (9
After 0 minutes, the reaction solution was poured into a large amount of water and washed by stirring, and the organic phase and the aqueous phase were separated to remove the catalyst. Further, the volatile components in the organic phase were removed to obtain a polymer product. The results of measuring the tensile strength of the obtained polymer are shown in Table 3.

Comparative Example 3 In a reaction vessel, 340 ml of butyl chloride as a solvent, 240 ml of hexane, 140 ml of isobutylene as a monomer, and p- as an initiator.
DCC 0.29 g, DMAc 0.2 as electron donor
Charge 0 g. A dry ice-ethanol bath is placed around the outer periphery of the reaction vessel and the temperature is brought to -75 ° C while stirring and mixing. The reaction is started by adding 4.9 ml of TiCl ₄ as a catalyst to the reaction vessel. After completion of the isobutylene reaction (after 90 minutes), styrene as a monomer was further added.
A block copolymerization reaction was carried out by adding 5 g. After the completion of the reaction (after 90 minutes), the reaction solution was poured into a large amount of water and washed by stirring, and the organic phase and the aqueous phase were separated to remove the catalyst. Further, the volatile components in the organic phase were removed to obtain a polymer product. The experimental results are shown in Table 3.

[0056]

[Table 3] As is clear from Example 3 and Comparative Example 3 described above, the method of the present invention can improve the tensile strength of the product polymer and can suppress the exothermic peak to about 1/2 as compared with the conventional method.

(Example 4) 65 kg of butyl chloride and 34 k of hexane were used as a solvent in a reaction vessel with a jacket.
g, 15 kg of isobutylene as a monomer, 0.05 kg of p-DCC as an initiator, DM as an electron donor
Charge 0.02 kg of Ac. The brine cooled in the refrigerator is circulated in the jacket of the reaction vessel, and the temperature is brought to −75 ° C. while stirring and mixing the inside of the reactor. TiC as catalyst
The reaction is initiated by the addition of l ₄ 0.9 kg of the reaction vessel. 50 minutes after the start of the reaction, TiCl ₄ 0.2 kg
And 0.005 kg of DMAc are added to continue the polymerization reaction. 75 minutes after the start of the reaction, 0.5 kg of TiCl ₄ was added.
And DMAc (0.01 kg) are added to continue the polymerization reaction. After completion of the reaction (after 135 minutes), 7 kg of styrene was further added as a monomer to carry out a block copolymerization reaction. After the completion of the reaction (after 105 minutes), the reaction solution was poured into a large amount of water and washed by stirring, and the organic phase and the aqueous phase were separated to remove the catalyst. Further, the volatile components in the organic phase were removed to obtain a polymer product. The experimental results are shown in Table 4.

Comparative Example 4 65 kg of butyl chloride and 34 k of hexane were used as a solvent in a jacketed reaction vessel.
g, 15 kg of isobutylene as a monomer, 0.05 kg of p-DCC as an initiator, DM as an electron donor
Charge 0.035 kg of Ac. The brine cooled in the refrigerator is circulated in the jacket of the reaction vessel, and the temperature is brought to −75 ° C. while stirring and mixing the inside of the reactor. Ti as catalyst
The reaction is started by adding 1.6 kg of Cl ₄ to the reaction vessel. After completion of the reaction (after 90 minutes), 7 kg of styrene was further added as a monomer to carry out a block copolymerization reaction. After the completion of the reaction (after 90 minutes), the reaction solution was poured into a large amount of water and washed by stirring, and the organic phase and the aqueous phase were separated to remove the catalyst. Further, the volatile components in the organic phase were removed to obtain a polymer product. The jacketed reaction vessel and refrigerator used are the same as in Example 3. The experimental results are shown in Table 4.

[0059]

[Table 4] As is clear from Example 4 and Comparative Example 4, the method of the present invention can improve the tensile strength of the product polymer as compared with the conventional method. Further, since the temperature rise peak can be reduced to about 1/2 and the heat removal load peak can be reduced to about 1/2, it is expected to reduce the equipment cost of the refrigerator process.

[0060]

As shown in the results of the above Examples and Comparative Examples, when the method for producing an isobutylene polymer proposed by the present invention is used, a polymer having a narrower molecular weight distribution than the conventional method is obtained. You can This has the effect of lowering the viscosity of the obtained liquid polymer, and can exhibit the characteristics of excellent workability in handling the product. Also,
By using the method of the present invention, a high strength isobutylene block copolymer can be obtained.

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Claims (16)

[Claims] 1. A method for producing an isobutylene-based polymer, characterized in that a polymerization catalyst and an electron donor are separately divided and sequentially added to a solution containing an isobutylene monomer and a polymerization initiator. 2. The method for producing an isobutylene-based polymer according to claim 1, wherein the polymerization catalyst and the electron donor are each divided and added successively in the range of 2 to 5 times. 3. The polymerization initiators are (1-chloro-1-methylethyl) benzene, 1,4-bis (1-chloro-1-methylethyl) benzene and 1,3,5-tris (1-chloro). The method for producing an isobutylene polymer according to claim 1, which is at least one selected from the group consisting of -1-methylethyl) benzene. 4. The method for producing an isobutylene polymer according to claim 1, wherein the polymerization catalyst is TiCl ₄ . 5. The electron donor is at least one selected from the group consisting of pyridine, 2-methylpyridine, trimethylamine, dimethylacetamide, dimethylsulfoxide, ethyl acetate and titanium tetraisopropoxide. 2. A method for producing an isobutylene polymer. 6. The electron donor is 2-methylpyridine and / or
Alternatively, the method for producing an isobutylene polymer according to claim 1, which is dimethylacetamide. 7. The isobutylene-based polymer according to any one of claims 1 to 4, wherein the total addition amount of the polymerization catalyst is 0.1 to 1000 times the number of moles based on the amount of the initiator. Production method. 8. The isobutylene polymer according to claim 1, wherein the total addition amount of the polymerization catalyst is 0.5 to 500 times the number of moles based on the amount of the initiator. Production method. 9. The method for producing an isobutylene polymer according to claim 1, wherein the total addition amount of the polymerization catalyst is 0.0001 to 10 times the molar number based on the amount of the isobutylene monomer. 10. The method for producing an isobutylene polymer according to claim 1, wherein the total addition amount of the polymerization catalyst is 0.001 to 1 times the number of moles based on the amount of the isobutylene monomer. 11. The isobutylene-based polymer according to claim 1, wherein the total amount of the electron donor added is 0.01 to 1 times the amount of the polymerization catalyst present in the reaction solution. Manufacturing method of coalescence. 12. The total amount of the electron donor added is 0.02 to 0.5 based on the amount of the polymerization catalyst present in the reaction solution.
The method for producing an isobutylene-based polymer according to any one of claims 1 to 6, wherein the amount is double. 13. The method for producing an isobutylene polymer according to claim 1, wherein the polymerization is initiated by first adding half or more of the total amount of the polymerization catalyst used in the polymerization reaction. 14. A liquid containing an isobutylene-based polymer obtained by the method according to claim 1, to which a cationically polymerizable monomer different from isobutylene is added to react with the isobutylene-based polymer. A method for producing an isobutylene block copolymer, comprising: 15. The method for producing an isobutylene block copolymer according to claim 14, wherein the cationically polymerizable monomer different from isobutylene is an aromatic vinyl compound. 16. The method for producing an isobutylene block copolymer according to claim 15, wherein the cationically polymerizable monomer other than isobutylene is styrene.