Method for producing (METH)acryloyl-terminated polyisobutylene

Abstract

The present invention pertains to a method for producing a (meth)acryloyl-terminated polyisobutylene, the method comprising: a step 1 for polymerizing a monomer component containing isobutylene in the presence of titanium(IV) chloride to obtain a halogen-terminated polyisobutylene; and a step 2 for reacting the halogen-terminated polyisobutylene obtained in the step 1 with a compound having a (meth)acryloyl group represented by general formula (1) to obtain a polyisobutylene having a (meth)acryloyl group represented by general formula (1) at the terminal thereof, wherein in the step 1, the polymerization reaction is performed in a batch manner, and the temperature of a polymerization reaction solution is -60ºC to -40ºC. (In general formula (1), R1 represents a hydrogen atom or a methyl group.)　Consequently, provided is a method which is for producing a (meth)acryloyl-terminated polyisobutylene and by which a (meth)acryloyl-terminated polyisobutylene having a low viscosity can be obtained.

Description

Method for producing (meth)acryloyl-terminated polyisobutylene

[0001] The present invention relates to a method for producing low viscosity (meth)acryloyl-terminated polyisobutylene.

[0002] Because polyisobutylene has excellent durability, heat resistance, weather resistance, water resistance, and gas barrier properties, (meth)acryloyl-terminated polyisobutylene is expected to be used in applications such as inks, paints, adhesives, sealants, precision parts for electrical and electronic applications, and shaped objects. Furthermore, (meth)acryloyl-terminated polyisobutylene can be crosslinked and cured by active energy rays such as ultraviolet (UV) rays and electron beams (EB). (Meth)acryloyl-terminated polyisobutylene is generally produced by cationic polymerization. For example, Patent Documents 1 and 2 describe the production of (meth)acryloyl-terminated polyisobutylene by cationic polymerization.

[0003] WO2013 / 047314 JP 2022-124977 A

[0004] However, (meth)acryloyl-terminated polyisobutylene produced by the production method described in Patent Document 1 has problems such as high viscosity and poor workability when used in inks, paints, adhesives, sealants, precision parts for electrical and electronic applications, and shaped objects. Furthermore, the continuous production method described in Patent Document 2 has problems such as complex equipment, cumbersome operation, and time-consuming maintenance. The present invention solves the above-mentioned conventional problems and provides a method for producing (meth)acryloyl-terminated polyisobutylene that can easily produce (meth)acryloyl-terminated polyisobutylene with a low viscosity.

[0005] The present invention relates to a method for producing (meth)acryloyl-terminated polyisobutylene, comprising: Step 1, polymerizing a monomer component containing isobutylene in the presence of titanium(IV) chloride to obtain halogen-terminated polyisobutylene; and Step 2, reacting the halogen-terminated polyisobutylene obtained in Step 1 with a compound having a (meth)acryloyl group represented by the following general formula (1) to obtain polyisobutylene having a (meth)acryloyl group at its terminal represented by the following general formula (1), wherein in Step 1, the polymerization reaction is carried out batchwise and the temperature of the polymerization reaction solution is between -60°C and -40°C. (However, in the general formula (1), R 1 represents a hydrogen atom or a methyl group.

[0006] According to the production method of the present invention, a (meth)acryloyl-terminated polyisobutylene having a low viscosity can be easily obtained.

[0007] The present inventors have conducted extensive research to solve the above-mentioned problems and have found that, when producing (meth)acryloyl-terminated polyisobutylene, low-viscosity (meth)acryloyl-terminated polyisobutylene can be easily obtained by polymerizing a monomer component containing isobutylene batchwise in the presence of titanium(IV) chloride and setting the polymerization temperature within a specific range.

[0008] However, the present invention is not limited to the following embodiments and various modifications may be made within the scope of the claims. Embodiments that combine technical means described in different embodiments are also included in the technical scope of the present invention.

[0009] Unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more and B or less." In this specification, "(meth)acrylic" means "acrylic and / or methacrylic." In this specification, "(meth)acryloyl" means "acryloyl and / or methacryloyl."

[0010] In one or more embodiments of the present invention, the (meth)acryloyl-terminated polyisobutylene can be produced by preparing a halogen-terminated polyisobutylene in step 1, and then reacting the halogen-terminated polyisobutylene with a compound having a (meth)acryloyl group in step 2.

[0011] Specifically, in step 1, a monomer component containing isobutylene is polymerized in the presence of titanium (IV) chloride to obtain halogen-terminated polyisobutylene.

[0012] The isobutylene-containing monomer component may contain only isobutylene, or may contain isobutylene and other monomers. From the viewpoint of easily obtaining a (meth)acryloyl-terminated polyisobutylene having balanced physical properties, the isobutylene-containing monomer component preferably contains 60 mol% to 100 mol% of isobutylene, more preferably 70 mol% to 100 mol%, even more preferably 80 mol% to 100 mol%, even more preferably 90 mol% to 100 mol%, even more preferably 95 mol% to 100 mol%, and may consist of 100 mol%.

[0013] The other monomer is not particularly limited as long as it is a cationically polymerizable monomer, and examples thereof include aliphatic olefins (1-butene, etc.); aromatic vinyls (styrene, methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, etc.); dienes (1,3-butadiene, isoprene, etc.); vinyl ethers (butyl vinyl ether, etc.); silanes (vinyltrimethylsilane, allyltrimethylsilane, etc.); terpenes (α-pinene, β-pinene, limonene, etc.); vinylcarbazole; and acenaphthylene. In terms of ease of copolymerization with isobutylene and favorable physical properties of the resulting copolymer, the other monomer is preferably one or more selected from the group consisting of 1-butene, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, 1,3-butadiene, isoprene, α-pinene, β-pinene, and limonene.

[0014] In step 1, the polymerization of the isobutylene-containing monomer component is carried out batchwise. As used herein, "batchwise" refers to initiating the polymerization reaction after all of the monomer components required for polymerization have been charged into a polymerization vessel or other polymerization apparatus. This allows for convenient polymerization of the isobutylene-containing monomer component. Furthermore, in step 1, the temperature of the polymerization reaction solution is adjusted to between -60°C and -40°C. This not only reduces energy costs but also, surprisingly, enables the production of a (meth)acryloyl-terminated polyisobutylene with a low viscosity. From the viewpoints of reducing energy costs and improving the physical properties of the (meth)acryloyl-terminated polyisobutylene, step 1 is preferably carried out at a higher temperature, in the range of between -55°C and -45°C. As used herein, "temperature of the polymerization reaction solution" refers to the temperature of the polymerization reaction solution at the start of polymerization.

[0015] Titanium(IV) chloride is a Lewis acid and functions as a polymerization catalyst. The polymerization reaction is preferably carried out in the presence of an electron donor. It is more preferable that the concentration of the electron donor in the polymerization reaction solution is 3 to 25 mM, and that the concentration of titanium(IV) chloride is 15 to 40 mM higher than the concentration of the electron donor. It is more preferable that the concentration of titanium(IV) chloride in the polymerization reaction solution is 17 to 35 mM higher than the concentration of the electron donor, and particularly preferably 18 to 30 mM higher. When the difference in concentration between titanium(IV) chloride and the electron donor is within the above-mentioned range, the polymerization rate can be appropriately adjusted and the β-proton elimination reaction in cationic polymerization can be effectively suppressed, even when the polymerization reaction is carried out at temperatures from -60 to -40°C.

[0016] In this specification, the concentration of titanium(IV) chloride in the polymerization reaction solution is calculated by the following formula (1) based on the "volume of the polymerization reaction solution" and the "number of moles of titanium(IV) chloride" at the end of the polymerization reaction of the monomer components including isobutylene. In the following formula (1), the "volume of the polymerization reaction solution" is the "total volume of all materials (including monomers, catalysts, solvents, etc.) used in the polymerization reaction." [Formula 1] [Concentration of titanium(IV) chloride in the polymerization reaction solution] = "number of moles of titanium(IV) chloride" (mmol) / "volume of the polymerization reaction solution" (L)

[0017] The electron donor is believed to have the effect of stabilizing the carbocation at the growing end during cationic polymerization. Using titanium(IV) chloride and an electron donor in combination tends to facilitate the production of polymers with narrow molecular weight distributions and controlled structures. By setting the electron donor concentration in the polymerization reaction solution to 3 to 25 mM, the polymerization rate can be appropriately adjusted and the β-proton elimination reaction in cationic polymerization can be suppressed, even when the polymerization reaction is carried out at higher temperatures, specifically, at temperatures between -60°C and -40°C. When the electron donor concentration is 3 mM or higher, the polymerization rate adjustment effect is not weakened when the polymerization reaction is carried out at temperatures between -60°C and -40°C, and the β-proton elimination reaction in cationic polymerization is easily suppressed. When the electron donor concentration is 25 mM or less, the polymerization rate is not too slow, and the polymerization does not take long, which facilitates reduction in energy costs. The electron donor concentration in the polymerization reaction solution is preferably 4 to 23 mM, and more preferably 5 to 20 mM.

[0018] In this specification, the concentration of the electron donor in the polymerization reaction solution is calculated by the following formula (2) based on the "volume of the polymerization reaction solution" and the "number of moles of the electron donor" at the end of the polymerization reaction of the monomer components including isobutylene. In the following formula (2), the "volume of the polymerization reaction solution" is the "total volume of all materials (including monomers, catalysts, solvents, etc.) used in the polymerization reaction." [Formula 2] [Concentration of the electron donor in the polymerization reaction solution] = "number of moles of the electron donor" (mmol) / "volume of the polymerization reaction solution" (L)

[0019] Examples of the electron donor include amine compounds, amide compounds, sulfoxide compounds, ester compounds, ether compounds, and metal compounds having an oxygen atom bonded to a metal atom. More specifically, compounds having a donor number, which is defined as a parameter representing the strength of various compounds as electron donors, of 15 to 60 can be preferably used.

[0020] As the amine compound, for example, a pyridine compound can be suitably used. Examples of the pyridine compound include 2-methylpyridine, 3-methylpyridine, 3,5-dimethylpyridine, 2,6-dimethylpyridine, 2,6-di-tert-butylpyridine, 2-tert-butylpyridine, and 2,4,6-trimethylpyridine. Examples of amine compounds other than the pyridine compound include diethylamine, trimethylamine, triethylamine, tributylamine, 1-methylpyrrolidine, 1-methylpiperidine, 1,4-diazabicyclo[2.2.2]octane, N,N,N',N'-tetraacetylethylenediamine, and N,N,N',N'-tetramethylethylenediamine.

[0021] Examples of the amide compounds include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, and hexamethylphosphoric triamide.

[0022] Examples of the sulfoxide compounds include dimethyl sulfoxide, and examples of the ether compounds include diethyl ether.

[0023] Examples of the ester compounds include methyl acetate, ethyl acetate, and trimethyl phosphate.

[0024] Examples of the metal compound include titanium alkoxides such as titanium (III) methoxide, titanium (IV) methoxide, titanium (IV) isopropoxide, and titanium (IV) butoxide, and aluminum alkoxides such as aluminum triethoxide and aluminum tributoxide.

[0025] The above electron donors may be used alone or in combination of two or more. Among them, amine compounds are preferred from the viewpoint of the effect of suppressing side reactions.

[0026] In step 1, the polymerization of the isobutylene-containing monomer component is preferably carried out in the presence of a compound represented by the following general formula (3), thereby producing a halogen-terminated polyisobutylene represented by the following general formula (4).

[0027] However, in the general formula (3), R 5 represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic hydrocarbon group, X represents a halogen atom, and n represents a natural number.

[0028] R in the general formula (3) 5 In the formula (I), specific examples of the aromatic hydrocarbon group include a cumyl group, an m-dicumyl group, a p-dicumyl group, a 5-tert-butyl-1,3-dicumyl group, a 5-methyl-1,3-dicumyl group, and a 1,3,5-tricumyl group. Specific examples of the aliphatic hydrocarbon group include groups represented by CH(CH)CCH(CH)C- and -(CH)CCH(CH)CCH(CH)C-. Of these, one or more selected from the group consisting of a cumyl group, an m-dicumyl group, a p-dicumyl group, a 5-tert-butyl-1,3-dicumyl group, CH(CH)CCH(CH)C-, and -(CH)CCH(CH)CCH(CH)C- are particularly preferred in terms of availability.

[0029] In the general formula (3), the halogen atom is specifically a chlorine atom, a bromine atom, or an iodine atom, but a chlorine atom is preferred in terms of availability and stability of the compound.

[0030] In the general formula (3), n is a natural number, but is preferably 2 or 3 in order to easily achieve sufficient strength, durability, gel fraction, etc. when obtaining a crosslinked polymer by a crosslinking reaction.

[0031] The compound represented by the general formula (3) functions as a polymerization initiator, and is thought to generate a carbocation in the presence of a Lewis acid, i.e., titanium (IV) chloride, and become the initiation point for cationic polymerization.

[0032] Specific examples of the compound represented by general formula (3) include (1-chloro-1-methylethyl)benzene [C6H5C(CH3)2Cl], 1,4-bis(1-chloro-1-methylethyl)benzene [1,4-Cl(CH3)2CC6H4C(CH3)2Cl], 1,3-bis(1-chloro-1-methylethyl)benzene [1,3-Cl(CH3)2CC6H4C(CH3)2Cl], 1,3,5-tris(1-chloro-1-methylethyl)benzene [1,3,5-(ClC(CH3)2)3C6H3], and 1,3-bis(1-chloro-1-methylethyl)-5-(tert-butyl)benzene [1,3-(C(CH3)2Cl)2-5-(C(CH3)3)C6H3]. Among these, one or more selected from the group consisting of 1,4-bis(1-chloro-1-methylethyl)benzene, 1,3-bis(1-chloro-1-methylethyl)benzene, and 1,3-bis(1-chloro-1-methylethyl)-5-(tert-butyl)benzene are preferred, and one or more bis(1-chloro-1-methylethyl)benzenes selected from the group consisting of 1,4-bis(1-chloro-1-methylethyl)benzene and 1,3-bis(1-chloro-1-methylethyl)benzene are more preferred. Note that bis(1-chloro-1-methylethyl)benzene is also known as bis(α-chloroisopropyl)benzene, bis(2-chloro-2-propyl)benzene, or dicumyl chloride, and 1,4-bis(1-chloro-1-methylethyl)benzene is also known as p-dicumyl chloride.

[0033] In the general formula (4), R 5 , X and n are the same as those in the general formula (3), and therefore, the explanation will be omitted here. In the general formula (4), A represents polyisobutylene.

[0034] In step 1, when the isobutylene-containing monomer component contains only isobutylene, A becomes a homopolymer of isobutylene. When the isobutylene-containing monomer component contains isobutylene and another monomer, A becomes a copolymer of isobutylene and another monomer. Examples of the other monomer include the other monomers described above. Specifically, from the viewpoint of balanced physical properties, A (polyisobutylene) preferably contains 60 mol% to 100 mol% of isobutylene-derived units, more preferably 70 mol% to 100 mol%, even more preferably 80 mol% to 100 mol%, even more preferably 90 mol% to 100 mol%, even more preferably 95 mol% to 100 mol%, and may even consist of 100 mol%. Furthermore, A (polyisobutylene) may contain 40 mol% or less, 30 mol% or less, 20 mol% or less, 10 mol% or less, or 5 mol% or less of other monomers.

[0035] In the halogen-terminated polyisobutylene represented by the general formula (4), the halogen may be located at the end of the main chain, or in the middle of the main chain, or at both. When located in the middle of the main chain, the halogen is included as a side chain. In one embodiment, the halogen is located only at the end of the main chain.

[0036] The polymerization reaction solution may further contain an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent generally used in cationic polymerization, and examples thereof include halogenated hydrocarbons, non-halogenated hydrocarbons such as aliphatic hydrocarbons and aromatic hydrocarbons, and mixtures thereof.

[0037] Examples of the halogenated hydrocarbon that can be used include methyl chloride, methylene chloride, chloroethane, dichloroethane, 1-chloropropane, 1-chloro-2-methylpropane, 1-chlorobutane (also referred to as butyl chloride), 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, and chlorobenzene. These may be used alone or in combination of two or more.

[0038] Examples of the aliphatic hydrocarbon include n-butane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, 2-methylpropane, 2-methylbutane, 2,3,3-trimethylpentane, 2,2,5-trimethylhexane, cyclohexane, methylcyclohexane, ethylcyclohexane, and paraffin oil. These may be used alone or in combination of two or more.

[0039] Examples of the aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, propylbenzene, and butylbenzene. These may be used alone or in combination of two or more.

[0040] Among these, from the viewpoints of solubility and economy, it is preferable to use, as the organic solvent, a mixed solvent of an aliphatic hydrocarbon and a halogenated hydrocarbon having 2 or more carbon atoms, or a mixed solvent of an aromatic hydrocarbon and a halogenated hydrocarbon having 2 or more carbon atoms, and it is more preferable to use a mixed solvent of an aliphatic hydrocarbon and a halogenated hydrocarbon having 2 to 5 carbon atoms, or a mixed solvent of an aromatic hydrocarbon and a halogenated hydrocarbon having 2 to 5 carbon atoms.

[0041] Taking into consideration the viscosity of the polymer solution and ease of heat removal, the organic solvent is preferably selected so that the concentration of the resulting polymer is 1 to 50% by weight, more preferably 1 to 30% by weight.

[0042] Next, in step 2, the halogen-terminated polyisobutylene obtained in step 1, preferably the halogen-terminated polyisobutylene represented by the general formula (4), is reacted with a compound having a (meth)acryloyl group.

[0043] The compound having a (meth)acryloyl group is preferably a compound having a (meth)acryloyl group and a phenoxy group represented by the following general formula (5).

[0044]

[0045] However, in the general formula (5), R 1 represents a hydrogen atom or a methyl group. 2 represents a divalent saturated hydrocarbon group having 2 to 6 carbon atoms and containing no heteroatoms. 3 , R 4 each independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group.

[0046] In the general formula (5), R 2 Specific examples of R include alkylene groups (methylene, propylene, butylene, pentylene, hexylene, etc.). From the viewpoint of availability and reactivity of raw materials, R 2 is preferably a butylene group or a pentylene group.

[0047] R in the general formula (5) 3 , R 4Regarding R, specific examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, a nonyl group, and a decanyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. From the viewpoint of reactivity, R 3 , R 4 are preferably each independently selected from the group consisting of a hydrogen atom, a methyl group, and a methoxy group. 3 , R 4 are more preferably all hydrogen atoms.

[0048] Specific examples of compounds having a (meth)acryloyl group and a phenoxy group represented by the general formula (5) include 2-phenoxyethyl (meth)acrylate, 3-phenoxypropyl (meth)acrylate, 4-phenoxybutyl (meth)acrylate, 5-phenoxypentyl (meth)acrylate, and 6-phenoxyhexyl (meth)acrylate. Among these, 2-phenoxyethyl (meth)acrylate, 3-phenoxypropyl (meth)acrylate, and 4-phenoxybutyl (meth)acrylate are more preferred from the viewpoint of reactivity, with 3-phenoxypropyl (meth)acrylate or 4-phenoxybutyl (meth)acrylate being even more preferred, and 3-phenoxypropyl acrylate (also referred to as phenoxypropyl acrylate) or 4-phenoxybutyl acrylate (also referred to as phenoxybutyl acrylate) being particularly preferred.

[0049] The compound having a (meth)acryloyl group and a phenoxy group represented by the general formula (5) may be a commercially available product and used as is, or may be synthesized by a known method.

[0050] An example of a method for synthesizing the compound having a (meth)acryloyl group and a phenoxy group is a method of reacting a compound represented by the following general formula (6), which is an alcohol compound, with a compound represented by the following general formula (7) (hereinafter also referred to as synthesis method 1).

[0051]

[0052]

[0053] In the general formulas (6) and (7), R 1 ~R 4 is defined as in the general formula (5). Y is a chlorine atom, a bromine atom or an iodine atom.

[0054] When reacting the compound represented by general formula (6) with the compound represented by general formula (7), a base may be added to the reaction system. This captures the generated HY (hydrogen chloride, hydrogen bromide, or hydrogen iodide) and promotes the reaction. Examples of the base include amine compounds and metal salts. Specific examples of the amine compounds include nitrogen-containing compounds such as ammonia, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-i-propylamine, tri-i-propylamine, di-n-butylamine, tri-n-butylamine, di-i-butylamine, tri-i-butylamine, pyridine, α-picoline, β-picoline, aniline, methylaniline, dimethylaniline, and N,N-dimethylaniline. Examples of the metal salts include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate, lithium hydride, sodium hydride, potassium hydride, butyllithium, and lithium diisopropylamide.

[0055] The system in which the compound represented by the general formula (6) and the compound represented by the general formula (7) are reacted may be a solvent system or a solvent-free system. The solvent used in the solvent system is preferably a dehydrated solvent. In this specification, a dehydrated solvent means a solvent having a water content of 100 ppm by weight or less.

[0056] Examples of the solvent include halogenated hydrocarbons (methylene chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride, n-butyl chloride, etc.); aromatic hydrocarbons (benzene, toluene, xylene, etc.); aliphatic hydrocarbons (pentane, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc.); ethers (diethyl ether, dibutyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, etc.); esters (ethyl acetate, etc.); and other solvents (acetone, dimethylformamide, acetonitrile, pyridine, triethylamine, etc.).

[0057] The reaction temperature when reacting the compound represented by the general formula (6) with the compound represented by the general formula (7) is usually from -70° C. to 200° C., preferably from 0° C. to 100° C. The reaction time is usually from 1 minute to 24 hours.

[0058] Another example of the synthesis method for the compound having a (meth)acryloyl group and a phenoxy group includes a method of reacting a compound having a phenoxy group and a halogen group and represented by the following general formula (8) with a compound represented by the following general formula (9):

[0059]

[0060]

[0061] In the general formulas (8) and (9), R 1 ~R 4 is defined as in the general formula (5). Y is a chlorine atom, a bromine atom or an iodine atom.

[0062] When the compound represented by the general formula (8) is reacted with the compound represented by the general formula (9), a base may be added to the reaction system. This captures the generated HY (hydrogen chloride, hydrogen bromide, or hydrogen iodide) and promotes the reaction. Examples of the base include those described in the section on Synthesis Method 1, and redundant description will be omitted.

[0063] Prior to reacting the compound represented by the general formula (8) with the compound represented by the general formula (9), the compound represented by the general formula (9) may be reacted with the above-mentioned base. In this case, the resulting neutralized product is reacted with the compound represented by the general formula (8).

[0064] When the compound represented by the general formula (8) is reacted with the compound represented by the general formula (9), a phase transfer catalyst may be added to the reaction system to promote the reaction. Examples of the phase transfer catalyst include tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium bromide.

[0065] The system in which the compound represented by the general formula (8) and the compound represented by the general formula (9) are reacted may be a solvent system or a solvent-free system. The solvent used in the solvent system is preferably a dehydrated solvent. Examples of the solvent include those described in the section on synthesis method 1, and duplicated descriptions will be omitted.

[0066] The reaction temperature when reacting the compound represented by the general formula (8) with the compound represented by the general formula (9) is usually from -70° C. to 200° C., preferably from 0° C. to 100° C. The reaction time is usually from 1 minute to 24 hours.

[0067] The compound represented by the general formula (8) may be a commercially available product and used as is. Alternatively, the compound represented by the general formula (8) may be synthesized by a known method.

[0068] An example of a method for synthesizing the compound represented by the general formula (8) is a method of reacting a compound represented by the following general formula (10) with a compound represented by the following general formula (11).

[0069]

[0070]

[0071] In the general formulas (10) and (11), R 2 ~R 4 The definition of is the same as in the case of the general formula (5). Y and Z are a chlorine atom, a bromine atom, or an iodine atom. Y and Z may be the same or different.

[0072] When the compound represented by the general formula (10) is reacted with the compound represented by the general formula (11), an alkali metal halide may be added to the reaction system to promote the reaction. Examples of the alkali metal halide include sodium iodide and potassium iodide.

[0073] When reacting the compound represented by the general formula (10) with the compound represented by the general formula (11), a base may be added to the reaction system to promote the reaction. Examples of the base include metal salts. Specific examples of the metal salts include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate, lithium hydride, potassium hydride, sodium hydride, butyllithium, and lithium diisopropylamide.

[0074] The system in which the compound represented by the general formula (10) and the compound represented by the general formula (11) are reacted may be a solvent system or a solvent-free system. The solvent used in the solvent system is preferably a dehydrated solvent. Examples of the solvent include those described in the section on synthesis method 1, and redundant explanations will be omitted.

[0075] The reaction temperature when reacting the compound represented by the general formula (10) with the compound represented by the general formula (11) is usually from -70° C. to 200° C., preferably from 0° C. to 100° C. The reaction time is usually from 1 minute to 24 hours.

[0076] The compound having a (meth)acryloyl group and a phenoxy group represented by the general formula (5) may be appropriately purified. The purification method is not particularly limited, and known methods can be used. Examples of the purification method include washing with water (the water may be acidic, alkaline, or neutral), and using an adsorbent.

[0077] In step 2, when reacting the halogen-terminated polyisobutylene represented by the general formula (4) with a compound having a (meth)acryloyl group, preferably a compound having a (meth)acryloyl group and a phenoxy group represented by the general formula (5), it is preferable to use a Lewis acid as a catalyst.

[0078] The Lewis acid used in step 2 is not particularly limited as long as it is a common Lewis acid, such as TiCl, Ti(OiPr), TiBr, AlCl, AlBr, EtAlCl, MeAlCl, EtAlCl, MeAlCl, EtAlBr, MeAlBr, EtAlBr, MeAlBr, EtAlBr, MeAlBr, Et 1.5 AlCl 1.5 , Me 1.5 AlCl 1.5 , Et 1.5 AlBr 1.5 , Me 1.5 AlBr 1.5 Lewis acids such as BCl, BF, BF(OEt), GaCl, FeCl, FeBr, SnCl, SnBr, SbCl, SbBr, SbF, WCl, TaCl, VCl, ZnCl, and ZnBr are preferred because they have particularly high reaction activity and good selectivity.

[0079] From the viewpoint of industrial availability and reactivity, TiCl, Ti(OiPr), TiBr, AlCl, AlBr, EtAlCl, MeAlCl, EtAlCl, MeAlCl, EtAlBr, MeAlBr, EtAlBr, MeAlBr, EtAlBr, MeAlBr, Et 1.5 AlCl 1.5 , Me 1.5 AlCl 1.5 , Et 1.5 AlBr 1.5, Me 1.5 AlBr 1.5 Particularly preferred are one or more selected from the group consisting of BCl3, BF3, BF3(OEt2), GaCl3, FeCl3, FeBr3, SnCl4, ZnCl2, and ZnBr2.

[0080] The reaction is preferably carried out under conditions where the molar ratio of the compound having a (meth)acryloyl group to the Lewis acid is less than 1.0. A molar ratio of less than 1.0 is preferable because the reactivity of the compound having a (meth)acryloyl group in the addition reaction with the halogen-terminated polyisobutylene is not reduced, and the introduction rate of the (meth)acryloyl group is not reduced. This is thought to be due to the compound having a (meth)acryloyl group coordinating with the Lewis acid, thereby reducing the Lewis acidity.

[0081] When reacting a compound having a (meth)acryloyl group with halogen-terminated polyisobutylene obtained by cationic polymerization, the reaction can be carried out under solvent-free conditions if the mixture of the halogen-terminated polyisobutylene and the compound having a (meth)acryloyl group has low viscosity, can be stirred, and can be reacted by itself.

[0082] On the other hand, a reaction solvent can also be used, for example, a single or mixed solvent arbitrarily selected from halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons.

[0083] The reaction temperature when reacting the halogen-terminated polyisobutylene with the compound having a (meth)acryloyl group is preferably lower than 0°C. Carrying out the reaction at a temperature lower than 0°C is preferred because there is no risk of a decrease in the introduction rate of the compound having a (meth)acryloyl group. This is because the halogen-terminated polyisobutylene undergoes a chain transfer reaction. Furthermore, from the viewpoint of energy reduction, the reaction temperature when reacting the halogen-terminated polyisobutylene with the compound having a (meth)acryloyl group in step 2 is more preferably −60°C or higher, and may be −60 to −40°C, or −55 to −45°C.

[0084] When reacting the halogen-terminated polyisobutylene with the compound having a (meth)acryloyl group, the halogen-terminated polyisobutylene may be isolated (i.e., steps 1 and 2 may be performed as two independent steps, with step 2 being performed after step 1 is completed), or the compound having a (meth)acryloyl group may be added to the polymerization system during polymerization of the halogen-terminated polyisobutylene (i.e., steps 1 and 2 may be performed consecutively or in parallel).

[0085] In the latter case, the timing for adding the compound having a (meth)acryloyl group is preferably when the conversion rate of isobutylene measured by gas chromatography has reached 50% or more, more preferably 80% or more, and even more preferably 95% or more, from the viewpoint of facilitating the production of a (meth)acryloyl-terminated polyisobutylene having a narrow molecular weight distribution. In this case, the completion of the polymerization reaction of the isobutylene-containing monomer component in step 1 refers to immediately before the addition of the "compound having a (meth)acryloyl group." In addition, in this case, both steps 1 and 2 are preferably carried out at -60 to -40°C, more preferably -55 to -45°C.

[0086] The method for producing (meth)acryloyl-terminated polyisobutylene according to one or more embodiments of the present invention may further include other steps in addition to steps 1 and 2. Examples of such other steps include a washing step, a purification step, and a solvent removal step, and these steps can be appropriately performed as needed. The washing step, purification step, and solvent removal step are not particularly limited and can be performed by selecting a known or conventional method. For example, in the washing step, the reaction solution containing the (meth)acryloyl-terminated polyisobutylene obtained in step 2 may be washed using a solvent such as water. In the purification step, impurities may be removed from the solution containing the (meth)acryloyl-terminated polyisobutylene using, for example, an adsorbent such as activated carbon and / or a filter. In the solvent removal step, the organic solvent, water, or other solvent may be removed from the solution containing the (meth)acryloyl-terminated polyisobutylene by a known or conventional method such as distillation. The removed organic solvent may be appropriately purified.

[0087] Distillation can be used as a method for further purifying the organic solvent used in polymerization. Distillation can remove almost all impurities with different boiling points. The distillation may be batch distillation or continuous distillation. For example, in the case of batch distillation, low-boiling impurities can be removed by withdrawing the overhead liquid at the beginning of the distillation, and high-boiling impurities can be removed by withdrawing the residual liquid at the bottom of the column after the distillation. In the case of continuous distillation, impurities can be removed using one or more distillation columns depending on the type of impurity to be removed.

[0088] By the production method according to one or more embodiments of the present invention, polyisobutylene having a (meth)acryloyl group represented by the following general formula (1) at its terminal (i.e., (meth)acryloyl-terminated polyisobutylene) can be obtained.

[0089]

[0090] However, in the general formula (1), R 1 represents a hydrogen atom or a methyl group. 1 When R is a hydrogen atom, the general formula (1) is an acryloyl group. 1 is a methyl group, the general formula (1) is a methacryloyl group.

[0091] In the (meth)acryloyl-terminated polyisobutylene, the (meth)acryloyl group represented by the general formula (1) may be located at the end of the main chain, in the middle of the main chain, or at both locations. When located in the middle of the main chain, the (meth)acryloyl group is included as a side chain. In the (meth)acryloyl-terminated polyisobutylene obtained by the production method of one or more embodiments of the present invention, the (meth)acryloyl group represented by the general formula (1) is preferably located only at the end of the main chain.

[0092] In the (meth)acryloyl-terminated polyisobutylene, the (meth)acryloyl group represented by the general formula (1) is more preferably represented by the following general formula (2):

[0093]

[0094] In the general formula (2), R 1 , R 2 , R 3 , and R 4 is the same as in the case of the general formula (5), and a duplicated explanation will be omitted here.

[0095] The number average molecular weight (Mn) of the (meth)acryloyl-terminated polyisobutylene is not particularly limited, but for example, the lower limit of the number average molecular weight (Mn) is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 3,000 or more, and particularly preferably 4,000 or more. The upper limit of the number average molecular weight (Mn) is preferably 500,000 or less, more preferably 150,000 or less, even more preferably 100,000 or less, and particularly preferably 50,000 or less. The weight average molecular weight (Mw) of the (meth)acryloyl-terminated polyisobutylene is not particularly limited, but for example, the lower limit of the weight average molecular weight (Mw) is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 3,000 or more, and particularly preferably 4,000 or more. The upper limit of the weight average molecular weight (Mw) is preferably 750,000 or less, more preferably 230,000 or less, even more preferably 150,000 or less, and particularly preferably 75,000 or less. If the molecular weight is within the above range, a cured product with sufficient strength is easily obtained. In this specification, the number average molecular weight and weight average molecular weight are determined by a standard polystyrene conversion method using size exclusion chromatography (SEC).

[0096] The molecular weight distribution (Mw / Mn) of the (meth)acryloyl-terminated polyisobutylene is preferably 1.8 or less, more preferably 1.5 or less, and even more preferably 1.3 or less. The lower limit of the molecular weight distribution may be 1.0 or more. When the molecular weight distribution is within the above range, a curable composition with high workability is easily obtained.

[0097] The average number (Fn) of (meth)acryloyl groups introduced per molecule of the (meth)acryloyl-terminated polyisobutylene is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and even more preferably 1.5 to 2.5, which makes the (meth)acryloyl-terminated polyisobutylene more susceptible to crosslinking and curing by active energy rays such as ultraviolet rays (UV) and electron beams (EB).

[0098] A polymerization inhibitor may be added to the (meth)acryloyl-terminated polyisobutylene, if necessary, during purification after polymerization or during storage. Examples of the polymerization inhibitor include phenolic compounds such as hydroquinone, hydroquinone monomethyl ether (also referred to as 4-methoxyphenol), p-tert-butylcatechol, 4-methoxy-naphthol, 2,6-di-t-butyl-4-methylphenol, 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,6-di-t-butyl-N,N-dimethylamino-p-cresol, 2,4-dimethyl-6-t-butylphenol, 4-t-butylcatechol, 4,4'-thio-bis(3-methyl-6-t-butylphenol), and 4,4'-butylidene-bis(3-methyl-6-t-butylphenol); 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl; 4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl; 4-benzoxyl N-oxy radical compounds such as 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine and 4-dihydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, and 2,2,6,6-tetramethylpiperidine-N-oxyl; amine compounds such as phenothiazine, N,N'-diphenyl-p-phenylenediamine, phenyl-β-naphthylamine, N,N'-di-β-naphthyl-p-phenylenediamine, and N-phenyl-N'-isopropyl-p-phenylenediamine; hydroxylamine compounds such as 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine and 4-dihydroxy-2,2,6,6-tetramethylpiperidine; quinone compounds such as benzoquinone and 2,5-di-t-butylhydroquinone; and copper compounds such as ferrous chloride and copper dimethyldithiocarbamate. These may be used alone or in combination of two or more.

[0099] Among the polymerization inhibitors, one or more selected from the group consisting of N-oxy radical compounds, phenolic compounds, amino compounds, and hydroxylamine compounds are preferred. Among these, from the viewpoint of effectively inhibiting polymerization, one or more selected from the group consisting of N-oxy radical compounds, N-oxy radical compounds, and phenolic compounds are more preferred. These preferred polymerization inhibitors can be used in combination with other polymerization inhibitors. When these preferred polymerization inhibitors are used in combination with other polymerization inhibitors, a more excellent polymerization inhibition effect can be obtained due to the synergistic effect of the combination of the two.

[0100] The amount of the polymerization inhibitor used is desirably 1 to 5,000 ppm by weight, preferably 50 to 3,000 ppm by weight, based on the (meth)acryloyl-terminated polyisobutylene, from the viewpoint of fully exhibiting the polymerization inhibiting effect.

[0101] The (meth)acryloyl-terminated polyisobutylene can be crosslinked and cured by active energy rays such as ultraviolet (UV) and electron beams (EB), and can be used in a variety of applications. Examples include sealants, pressure-sensitive adhesives, sealing materials, gasket materials, adhesives, coating materials, covering materials, resist materials, vibration-insulating materials, vibration-damping materials, shock-absorbing materials, buffer materials, electrical insulating materials, foams, paints, inks, casting agents, potting agents, molding materials, underfill materials, die-bonding materials, and fillers. Specific examples of parts in which the cured product can be used include electrical and electronic components (LEDs, batteries, fuel cells, secondary batteries, sensors, semiconductors, circuit boards, displays, home appliances, optical communications / optical circuits, optical recording, and magnetic recording), pharmaceuticals and medical products, automotive and marine components, building components, and acoustic components. The cured product can be in the form of, for example, a sheet (film), a tape, or a molded product (packing, O-rings, belts, tubes, valves, hoses, and the like). The (meth)acryloyl-terminated polyisobutylene has a low viscosity and is easy to work with when used in the above-mentioned applications.

[0102] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0103] [Measurement Method] (1) Molecular Weight The number average molecular weight (Mn) of (meth)acryloyl-terminated polyisobutylene was measured by a standard polystyrene conversion method using size exclusion chromatography (SEC). The SEC specifications are as follows: SEC system: HLC-8320 (Tosoh Corporation) Stationary phase: TSKgel Super HM-H (Tosoh Corporation) Mobile phase: Chloroform (2) Number of (meth)acryloyl Groups The average number (Fn) of (meth)acryloyl groups introduced per molecule of (meth)acryloyl-terminated polyisobutylene was determined by the following procedure. (a) The number average molecular weight (Mn) of (meth)acryloyl-terminated polyisobutylene was measured by the method described in (1). (b) The (meth)acryloyl-terminated polyisobutylene was 1 HNMR was measured. First, the area of ​​the peaks assigned to the two methyl groups in the isobutylene skeleton was used as the reference area. Specifically, the integral value of the peak near 1.3 ppm was set to satisfy the following formula: integral value of the peak near 1.3 ppm = (Mn / 56.11) x 6. Next, the peaks appearing near 5.8-5.9 ppm, near 6.1-6.2 ppm, and near 6.4 ppm were designated as peaks attributable to (meth)acryloyl groups. The integral value of each peak was calculated as a relative value to the reference area, and the average of the three integral values ​​was calculated. The obtained average value was designated as the average number of (meth)acryloyl groups introduced per molecule of polyisobutylene. (3) Viscosity The viscosity of the (meth)acryloyl-terminated polyisobutylene at 23°C was measured using a Toki Sangyo cone-plate viscometer TVE-25H.

[0104] Example 1 A 1-L separable flask was used as a polymerization vessel. After the atmosphere inside the polymerization vessel was replaced with nitrogen, 428 mL of a mixed solvent of butyl chloride and n-hexane in a volume ratio of 9:1 was added to the polymerization vessel using a syringe. Next, the polymerization vessel was immersed in dry ice / equine to cool to -50°C, and 159 mL (1.68 mol) of isobutylene was added to the polymerization vessel. Next, 0.33 mL (2.8 mmol) of 2,6-lutidine was added to the polymerization vessel. Next, 12.4 g of a 15 wt% p-dicumyl chloride solution of butyl chloride (p-dicumyl chloride: 8.05 mmol) and 10 mL of a mixed solvent of butyl chloride and n-hexane in a volume ratio of 9:1 were added to the polymerization vessel. Next, after confirming that the solution in the polymerization vessel had cooled to -50°C, 1.76 mL (16.1 mmol) of titanium(IV) chloride was added to the polymerization vessel to initiate the polymerization reaction. The temperature of the solution in the polymerization vessel (polymerization reaction solution) at the start of the polymerization reaction was minus 53°C. The polymerization solution was sampled at regular intervals during the reaction, and the isobutylene consumption rate was measured by gas chromatography. It was confirmed that 99.9 mol% of the isobutylene had been consumed 75 minutes after the addition of titanium(IV) chloride. Next, 4.08 g (18.5 mmol) of 4-phenoxybutyl acrylate and 5.29 mL (48.3 mmol) of titanium(IV) chloride were added to the polymerization vessel, and stirring was continued for 2 hours. The entire reaction solution was poured into an aqueous sodium hydroxide solution (a mixture of 577 g of pure water and 25.1 g of 48 wt% aqueous sodium hydroxide solution) heated to 50°C. The polymerization vessel was then rinsed with 112 g of a mixed solvent of butyl chloride and n-hexane in a volume ratio of 9:1. The reaction was then terminated by vigorously stirring for 60 minutes. After the reaction was terminated, the reaction solution was washed with 149 g of pure water. The reaction solution was then washed with 149 g of pure water. 8.3 g of powdered activated carbon (Taiko A, Futamura Chemical Co., Ltd.) was added to the washed reaction solution, which was then stirred for 30 minutes and filtered through a 1 μm filter. 0.17 g of 4-methoxyphenol (1700 ppm by weight of acryloyl-terminated polyisobutylene) was added to the resulting filtrate, and the solvent was distilled off at 120°C under reduced pressure to obtain acryloyl-terminated polyisobutylene that was liquid at room temperature (20±5°C).

[0105] Example 2 A 1-L separable flask was used as a polymerization vessel. After the atmosphere inside the polymerization vessel was replaced with nitrogen, 428 mL of a mixed solvent of butyl chloride and n-hexane in a volume ratio of 9:1 was added to the polymerization vessel using a syringe. Next, the polymerization vessel was immersed in dry ice / equine to cool to -50°C, and 159 mL (1.68 mol) of isobutylene was added to the polymerization vessel. Next, 0.33 mL (2.8 mmol) of 2,6-lutidine was added to the polymerization vessel. Next, 12.4 g of a 15 wt% p-dicumyl chloride solution of butyl chloride (p-dicumyl chloride: 8.05 mmol) and 10 mL of a mixed solvent of butyl chloride and n-hexane in a volume ratio of 9:1 were added to the polymerization vessel. Next, after confirming that the solution in the polymerization vessel had cooled to -50°C, 0.88 mL (8.0 mmol) of titanium(IV) chloride was added to the polymerization vessel to initiate the polymerization reaction. The temperature of the solution in the polymerization vessel (polymerization reaction solution) at the start of the polymerization reaction was minus 51°C. The polymerization solution was sampled from time to time during the reaction, and the isobutylene consumption rate was measured by gas chromatography. Twenty minutes after the addition of titanium(IV) chloride, 0.88 mL (8.0 mmol) of titanium(IV) chloride was further added. Ninety-five minutes after the initial addition of titanium(IV) chloride, it was confirmed that 99.9 mol% of the isobutylene had been consumed. Next, 4.08 g (18.5 mmol) of 4-phenoxybutyl acrylate and 5.29 mL (48.3 mmol) of titanium(IV) chloride were added to the polymerization vessel, and stirring was continued for 2 hours. The entire reaction solution was poured into an aqueous sodium hydroxide solution (a mixture of 577 g of pure water and 25.1 g of 48 wt % aqueous sodium hydroxide solution) heated to 50°C, and the washings obtained by washing the inside of the polymerization vessel with 112 g of a mixed solvent of butyl chloride and n-hexane in a volume ratio of 9:1 were added, followed by vigorously stirring for 60 minutes to terminate the reaction. After the reaction was terminated, the reaction solution was washed with 149 g of pure water. The reaction solution was further washed with 149 g of pure water. 8.3 g of powdered activated carbon (Taiko A, Futamura Chemical Co., Ltd.) was added to the washed reaction solution, which was stirred for 30 minutes and then filtered through a filter with 1 μm mesh.To the obtained filtrate was added 0.17 g (1700 ppm by weight of the acryloyl-terminated polyisobutylene) of 4-methoxyphenol, and the solvent was distilled off at 120°C under reduced pressure to obtain acryloyl-terminated polyisobutylene that was liquid at room temperature (20±5°C).

[0106] Example 3 A 1-L separable flask was used as a polymerization vessel. After the atmosphere inside the polymerization vessel was replaced with nitrogen, 428 mL of a mixed solvent of butyl chloride and n-hexane in a volume ratio of 9:1 was added to the polymerization vessel using a syringe. Next, the polymerization vessel was immersed in dry ice / equine to cool to -50°C, and 159 mL (1.68 mol) of isobutylene was added to the polymerization vessel. Next, 0.98 mL (8.5 mmol) of 2,6-lutidine was added to the polymerization vessel. Next, 12.4 g of a 15 wt% p-dicumyl chloride solution of butyl chloride (p-dicumyl chloride: 8.05 mmol) and 10 mL of a mixed solvent of butyl chloride and n-hexane in a volume ratio of 9:1 were added to the polymerization vessel. Next, after confirming that the solution in the polymerization vessel had cooled to -50°C, 1.19 mL (10.9 mmol) of titanium(IV) chloride was added to the polymerization vessel to initiate the polymerization reaction. The temperature of the solution in the polymerization vessel (polymerization reaction solution) at the start of the polymerization reaction was minus 51°C. The polymerization solution was sampled from time to time during the reaction, and the isobutylene consumption rate was measured by gas chromatography. Forty minutes after the addition of titanium(IV) chloride, an additional 1.19 mL (10.9 mmol) of titanium(IV) chloride was added. It was confirmed that 99.7 mol% of the isobutylene had been consumed 110 minutes after the initial addition of titanium(IV) chloride. Next, 4.08 g (18.5 mmol) of 4-phenoxybutyl acrylate and 5.29 mL (48.3 mmol) of titanium(IV) chloride were added to the polymerization vessel, and stirring was continued for 2 hours. The entire reaction solution was poured into an aqueous sodium hydroxide solution (a mixture of 575 g of pure water and 27.1 g of 48 wt % aqueous sodium hydroxide solution) heated to 50°C, and the washings obtained by washing the inside of the polymerization vessel with 112 g of a mixed solvent of butyl chloride and n-hexane in a volume ratio of 9:1 were added, followed by vigorously stirring for 60 minutes to terminate the reaction. After the reaction was terminated, the reaction solution was washed with 149 g of pure water. The reaction solution was further washed with 149 g of pure water. 8.3 g of powdered activated carbon (Taiko A, Futamura Chemical Co., Ltd.) was added to the washed reaction solution, which was stirred for 30 minutes and then filtered through a filter with 1 μm mesh.To the obtained filtrate was added 0.17 g (1700 ppm by weight of the acryloyl-terminated polyisobutylene) of 4-methoxyphenol, and the solvent was distilled off at 120°C under reduced pressure to obtain acryloyl-terminated polyisobutylene that was liquid at room temperature (20±5°C).

[0107] Comparative Example 1 A 1-L separable flask was used as a polymerization vessel. After the atmosphere inside the polymerization vessel was replaced with nitrogen, 428 mL of a mixed solvent of butyl chloride and n-hexane at a volume ratio of 9:1 was added to the polymerization vessel using a syringe. Next, the polymerization vessel was immersed in dry ice / equine at -50°C to cool, and 159 mL (1.68 mol) of isobutylene was added to the polymerization vessel. Next, 0.33 mL (2.8 mmol) of 2,6-lutidine was added to the polymerization vessel. Next, 12.4 g of a 15 wt% p-dicumyl chloride solution of butyl chloride (p-dicumyl chloride: 8.05 mmol) and 10 mL of a mixed solvent of butyl chloride and n-hexane at a volume ratio of 9:1 were added to the polymerization vessel. Next, after confirming that the solution in the polymerization vessel had cooled to -70°C, 0.88 mL (8.0 mmol) of titanium(IV) chloride was added to the polymerization vessel to initiate the polymerization reaction. The temperature of the solution in the polymerization vessel (polymerization reaction solution) at the start of the polymerization reaction was minus 75°C. The polymerization solution was sampled at regular intervals during the reaction, and the isobutylene consumption rate was measured by gas chromatography. It was confirmed that 99.9 mol% of the isobutylene had been consumed 75 minutes after the addition of titanium(IV) chloride. Next, 4.08 g (18.5 mmol) of 4-phenoxybutyl acrylate and 5.29 mL (48.3 mmol) of titanium(IV) chloride were added to the polymerization vessel, and stirring was continued for 2 hours. The entire reaction solution was poured into an aqueous sodium hydroxide solution (a mixture of 549 g of pure water and 22.1 g of 48 wt% aqueous sodium hydroxide solution) heated to 50°C. The polymerization vessel was then rinsed with 107 g of a mixed solvent of butyl chloride and n-hexane in a volume ratio of 9:1. The reaction was then terminated by vigorously stirring for 60 minutes. After the reaction was terminated, the reaction solution was washed with 141 g of pure water. The reaction solution was then washed with 141 g of pure water. 8.3 g of powdered activated carbon (Taiko A, Futamura Chemical Co., Ltd.) was added to the washed reaction solution, which was then stirred for 30 minutes and filtered through a filter with 1 μm mesh size. 0.17 g of 4-methoxyphenol (1700 ppm by weight of acryloyl-terminated polyisobutylene) was added to the resulting filtrate, and the solvent was distilled off at 120°C under reduced pressure to obtain acryloyl-terminated polyisobutylene that was liquid at room temperature (20±5°C).

[0108] The molecular weight, the average number of acryloyl groups introduced per molecule (Fn), and the viscosity of the acryloyl-terminated polyisobutylenes obtained in the Examples and Comparative Examples were measured as described above, and the results are shown in the following Table 1. Table 1 also shows the concentrations of titanium(IV) chloride and the electron donor in step 1, the concentration difference (= concentration of titanium(IV) chloride - concentration of electron donor), and the temperature of the polymerization reaction solution in step 1 (polymerization temperature).

[0109]

[0110] As can be seen from the results in Table 1, in the Examples in which the polymerization reaction of the isobutylene-containing monomer component was carried out batchwise and the temperature of the polymerization reaction solution was adjusted to between -60° C. and -40° C., a low-viscosity (meth)acryloyl-terminated polyisobutylene was easily obtained. On the other hand, in Comparative Example 1 in which the temperature of the polymerization reaction solution was lower than -60° C., the viscosity was about 35% higher than in the Examples.

[0111] One or more embodiments of the present invention may include, but are not limited to, the following embodiments, for example.

[0112] [1] A method for producing (meth)acryloyl-terminated polyisobutylene, comprising: Step 1, polymerizing a monomer component containing isobutylene in the presence of titanium (IV) chloride to obtain halogen-terminated polyisobutylene; and Step 2, reacting the halogen-terminated polyisobutylene obtained in Step 1 with a compound having a (meth)acryloyl group represented by the following general formula (1) to obtain polyisobutylene having a (meth)acryloyl group represented by the following general formula (1) at its terminal; wherein in Step 1, the polymerization reaction is carried out batchwise and the temperature of the polymerization reaction solution is between -60°C and -40°C. (However, in the general formula (1), R 1represents a hydrogen atom or a methyl group.) [2] The method for producing polyisobutylene according to [1], wherein in step 1, polymerization of the monomer component containing isobutylene is further carried out in the presence of an electron donor, and the concentration of the electron donor in the polymerization reaction solution is 3 to 25 mM, and the concentration of the titanium(IV) chloride is 15 to 40 mM higher than the concentration of the electron donor. [3] The method for producing (meth)acryloyl-terminated polyisobutylene according to [1] or [2], wherein in step 1, polymerization of the monomer component containing isobutylene is further carried out in the presence of a compound represented by the following general formula (3): (However, in the general formula (3), R 5 represents a monovalent or polyvalent aromatic hydrocarbon group, or a monovalent or polyvalent aliphatic hydrocarbon group, X represents a halogen atom, and n represents a natural number.) [4] The method for producing (meth)acryloyl-terminated polyisobutylene according to [2], wherein the electron donor is an amine compound. [5] The method for producing (meth)acryloyl-terminated polyisobutylene according to any of [1] to [4], wherein the compound having a (meth)acryloyl group represented by general formula (1) is a compound having a (meth)acryloyl group and a phenoxy group represented by the following general formula (5): (However, in the general formula (5), R 1 represents a hydrogen atom or a methyl group, R 2 represents a divalent saturated hydrocarbon group having 2 to 6 carbon atoms and containing no heteroatoms, and R 3 , R 4 each independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group.) [6] The method for producing (meth)acryloyl-terminated polyisobutylene according to any one of [1] to [5], wherein the solvent used in step 1 is a mixed solvent of an aliphatic hydrocarbon and a halogenated hydrocarbon having 2 or more carbon atoms, or a mixed solvent of an aromatic hydrocarbon and a halogenated hydrocarbon having 2 or more carbon atoms.

Claims

1. A method for producing (meth)acryloyl-terminated polyisobutylene, comprising: Step 1, polymerizing a monomer component containing isobutylene in the presence of titanium (IV) chloride to obtain halogen-terminated polyisobutylene; and Step 2, reacting the halogen-terminated polyisobutylene obtained in Step 1 with a compound having a (meth)acryloyl group represented by the following general formula (1) to obtain polyisobutylene having a (meth)acryloyl group at its terminal represented by the following general formula (1), wherein in Step 1, the polymerization reaction is carried out batchwise and the temperature of the polymerization reaction solution is between -60°C and -40°C. (However, in the general formula (1), R 1 represents a hydrogen atom or a methyl group.

2. The method for producing polyisobutylene according to claim 1, wherein in step 1, the polymerization of the monomer components containing isobutylene is further carried out in the presence of an electron donor, the concentration of the electron donor in the polymerization reaction solution is 3 to 25 mM, and the concentration of the titanium (IV) chloride is 15 to 40 mM higher than the concentration of the electron donor.

3. The method for producing a (meth)acryloyl-terminated polyisobutylene according to claim 1 or 2, wherein in step 1, the polymerization of the monomer component containing isobutylene is further carried out in the presence of a compound represented by the following general formula (3): (However, in the general formula (3), R 5 represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic hydrocarbon group, X represents a halogen atom, and n represents a natural number.

4. The method for producing (meth)acryloyl-terminated polyisobutylene according to claim 2, wherein the electron donor is an amine compound.

5. The method for producing (meth)acryloyl-terminated polyisobutylene according to claim 1 or 2, wherein the compound having a (meth)acryloyl group represented by general formula (1) is a compound having a (meth)acryloyl group and a phenoxy group represented by the following general formula (5): (However, in the general formula (5), R 1 represents a hydrogen atom or a methyl group, R 2 represents a divalent saturated hydrocarbon group having 2 to 6 carbon atoms and containing no heteroatoms, and R 3 , R 4 each independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group.

6. The method for producing (meth)acryloyl-terminated polyisobutylene according to claim 1 or 2, wherein the solvent used in step 1 is a mixed solvent of an aliphatic hydrocarbon and a halogenated hydrocarbon having two or more carbon atoms, or a mixed solvent of an aromatic hydrocarbon and a halogenated hydrocarbon having two or more carbon atoms.

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