JPH09208623A - Preparation of isobutylene polymer having functional group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To introduce a functional group with good productivity by mixing an alkenyl-terminated isobutylene polymer with a plasticizer in an inert gas atmosphere and reacting the mixture with a hydrosilyl-contg. compd. in the presence of a platinum catalyst. SOLUTION: An isobutylene polymer contg. at least one terminal alkenyl group and having a no. average mol.wt. of 500 to 200,000 (e.g. an isobutylene polymer contg. a terminal vinyl group) is mixed with a plasticizer (e.g. a paraffin plasticizer) in an inert gas atmosphere. The mixture is then reacted with a compd. represented by the formula (wherein R<1> and R<2> represent a 1-20C alkyl, a 6-20C aryl, or an (R')3 SiO group ; R' represents H or a 1-20C monovalent hydrocarbon; X represents a hydroxyl group, a halogen, an alkoxyl, or an acyloxyl; (a) is 0 to 3; (b) is 0 to 2; and (m) is 0 to 18) (e.g. dimethoxymethylsilane) in the presence of a platinum catalyst to prepare an isobutylene polymer having a functional group. This method can inhibit the formation of a reaction inhibitor, thus permitting the hydrosilylation to stably proceed.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an isobutylene polymer having a functional group, more specifically,
The present invention relates to a method for producing an isobutylene-based polymer having a functional group that is subjected to a hydrosilylation reaction by mixing the isobutylene-based polymer with a plasticizer under a platinum catalyst.

[0002]

Polymers having a functional group such as a vinyl group at the end can be used as a photocurable resin, a UV curable resin, an electron beam curable resin, etc. It is useful as a raw material for modifiers, coating materials, and sealing materials for construction. Among these, an isobutylene-based polymer having a terminal alkenyl group can be reacted with a hydrosilyl group-containing compound to form a moisture-curable polymer, which can be used as an adhesive, a pressure-sensitive adhesive, a paint, a sealing material, a waterproof material. It is used for timber and other purposes.

As a method for reacting an isobutylene-based polymer having a terminal functional group with a hydrosilyl group-containing compound, several methods have been conventionally known. For example, when the isobutylene-based polymer is a liquid having a low molecular weight and a low viscosity at room temperature, it is mixed with a hydrosilyl group-containing compound under heating without a solvent and using a platinum catalyst. When the molecular weight of the isobutylene-based polymer is high and has a high viscosity at room temperature or is solid due to crystallinity, etc., after isobutylene-based polymer is dissolved in a non-reactive good solvent and liquefied to have a low viscosity, Alternatively, after mixing with a plasticizer to reduce the viscosity, the hydrosilyl group-containing compound and the platinum catalyst are mixed and reacted under heating, and after the reaction, the solvent and unreacted components are distilled off to obtain the desired product. A method for obtaining the same is known.

Further, in these methods, particularly on an industrial scale, from the viewpoint of ensuring safety, the method of replacing the gas phase part of the reactor with an inert gas such as nitrogen or helium is carried out. desirable.

However, when an isobutylene polymer having at least one terminal alkenyl group in the molecule is subjected to a hydrosilylation reaction under a platinum catalyst, the gas phase part of the reactor is treated with an inert gas such as nitrogen or helium. When it is carried out by substitution, the catalytic activity in the reaction is remarkably reduced, and the hydrosilylation reaction rate becomes extremely slow. As a result, the reaction takes several days, which leads to extremely low productivity and a low functional group content, which leads to problems in product quality because desired physical properties cannot be obtained. This problem is believed to be overcome by using oxygen as a co-catalyst for the hydrosilylation reaction.

Furthermore, it has been reported so far that dissolved oxygen is a cocatalyst for the hydrosilylation reaction. For example,
J. Org. Chem. , 52, 4118 (198
7); Am. Chem. Soc. , 112, 599
8 (1990); as disclosed in JP-A-5-213972, etc., when a platinum catalyst is used, 1-
Reaction of 1-alkenes such as octene with triethylsilane, methyldioctylsilane, trioctylsilane, dioctylsilane with alkyl, dialkyl or trialkyls, reaction between triethylsilane and vinyltrimethylsilane or vinyltrichlorosilane, cyclohexene and methyl Reaction with dichlorosilane, reaction with 1-hexene or cyclohexene with methyldichlorosilane, reaction with 1-hexene with dimethoxymethylsilane, 1,1,1,
Reaction of 2,3,3,3-heptamethyltrisiloxane and 1-hexene or trans-2-hexene, reaction of triethylsilane and trans-2-hexene, reaction of trichlorosilane and 1,5-hexadiene, etc. At
It has been confirmed that dissolved oxygen in the reaction system acts as a cocatalyst for the reaction.

[0007]

The influence of such dissolved oxygen is not affected even when the isobutylene polymer having at least one terminal alkenyl group in the molecule is subjected to a hydrosilylation reaction under a platinum catalyst. It was revealed that the effect of dissolved oxygen as a co-catalyst can be recognized even under the so-called plasticizer system conditions in which agents are mixed. However, when the hydrosilylation reaction is carried out in a plasticizer system, when a petroleum-based softening agent which is usually used as a plasticizer is used, the plasticizer is oxidized by oxygen to cause carbonyl, alcohol, ester, or peroxide. The present inventors have confirmed that a phenomenon in which free acid or the like is generated, the hydrosilylation reaction is inhibited, and the reaction does not proceed further. In particular, when an isobutylene polymer and a plasticizer are mixed at a high temperature in the presence of oxygen, the plasticizer generates a radical by heat, and this radical is oxidized by oxygen to carbonyl, alcohol, ester, or peroxide. It was found that the hydrosilylation reaction was inhibited by generating free acid and the like.

Therefore, in carrying out the hydrosilylation reaction of an isobutylene polymer in a plasticizer system which is important from an industrial point of view, carbonyl, alcohol, ester, peroxide, free acid, etc. which are inhibitors of the hydrosilylation reaction. There has been a strong demand for establishment of a production method capable of suppressing the formation of hydrogen chloride and allowing the hydrosilylation reaction to proceed stably.

In view of the above situation, the present invention is a method for producing an isobutylene polymer having a functional group for carrying out a hydrosilylation reaction of an isobutylene polymer in a plasticizer system, which is an inhibitor of the hydrosilylation reaction. Some carbonyl,
It is an object of the present invention to provide a production method capable of suppressing the production of alcohols, esters, peroxides, free acids and the like and allowing the hydrosilylation reaction to proceed stably.

[0010]

As a result of intensive studies, the present inventors conducted a hydrosilylation reaction of an isobutylene-based polymer with a plasticizer system to produce an isobutylene-based polymer having a functional group. As a result, they have found that mixing a plasticizer and an isobutylene-based polymer in an inert gas atmosphere can suppress the formation of a reaction inhibitor, and have completed the present invention. That is, the gist of the present invention is to mix an isobutylene-based polymer containing at least one terminal alkenyl group and having a number average molecular weight of 500 to 200,000 with a plasticizer in an inert gas atmosphere, and then using a platinum catalyst. Then the general formula (I)

[0011]

Embedded image

(In the formula, R ¹ and R ² are the same or different and are an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a (R ′) ₃ SiO— group (in the formula: , R '
Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or hydrogen). X represents a hydroxyl group, a halogen, an alkoxyl group or an acyloxyl group, and when two or more are bonded, they may be the same or different. a represents the integer of 0-3. b represents an integer of 0 to 2. m represents an integer of 0-18. In the process of producing an isobutylene-based polymer having a functional group by reacting with a compound represented by the formula (1). Hereinafter, the present invention will be described in detail.

In the present invention, the isobutylene polymer is mixed with a plasticizer, and the isobutylene polymer is mixed with an inert gas prior to reacting with the compound represented by the general formula (I) under a platinum catalyst. Mix with plasticizer in atmosphere.

The inert gas atmosphere preferably has an oxygen concentration of 0.01% or less. Oxygen concentration is 0.
If it exceeds 01%, the effect of suppressing the production of reaction-inhibiting substances decreases. More preferably, it is 0.001% or less. When the isobutylene polymer and the plasticizer are mixed in the above inert gas atmosphere, the mixing temperature is preferably 10 to 300 ° C. When the mixing temperature is lower than 10 ° C, the viscosity of the isobutylene-based polymer is high and it becomes difficult to handle, and when the mixing temperature exceeds 300 ° C, the heating loss of the mixture increases. More preferably, it is 30 to 200 ° C.

In the present invention, the effect of dissolved oxygen can be avoided by mixing the isobutylene polymer and the plasticizer in the above-mentioned inert gas atmosphere prior to the start of the hydrosilylation reaction, and the hydrosilylation can be avoided. It is possible to suppress the production of a carbonyl compound that is a reaction inhibitor before the initiation of the oxidization reaction. As a result, the hydroxylation reaction can be stably started, and the reaction can proceed stably without stopping halfway.

The isobutylene polymer used in the present invention contains at least one terminal alkenyl group. The isobutylene-based polymer may be one having isobutylene as a main chain skeleton and containing a terminal alkenyl group active in the hydrosilylation reaction.

The method for producing the above isobutylene polymer is not particularly limited, and all known production methods can be effectively applied. Specifically, for example, US Pat.
According to the inifer method disclosed in Japanese Patent No. 276394, 1,4-bis (α-chloroisopropyl) benzene or 1,3,5-tris (α-chloroisopropyl) and isobutylene are used as benzene initiators and catalysts. As an end-functional polymer, an isobutylene-based polymer having a chlorine atom bonded to a tertiary carbon atom is produced by cationically polymerizing boron trichloride as a vinyl chloride. Based on
It can be produced by a method using allyltrimethylsilane disclosed in JP-A-3-105005; a method using a non-conjugated diene disclosed in JP-A-4-288309, or the like.

The isobutylene-based polymer used in the present invention is used in the fields of application of the isobutylene-based polymer having a functional group, such as adhesives, pressure-sensitive adhesives, paints, sealing materials, waterproof materials, weather resistance and heat resistance. In the case of use for the purpose of properties such as moisture resistance and gas barrier property, a copolymer containing an isobutylene unit as a main component is preferable. The content of isobutylene in the copolymer is preferably 51 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more.

In the above copolymer, examples of the monomer to be copolymerized with isobutylene include a cationically polymerizable monomer copolymerizable with isobutylene. As such a thing, for example, carbon number 5
12 olefins, C 5-12 conjugated dienes,
Non-conjugated dienes having 5 to 12 carbon atoms, vinyl ethers having 5 to 12 carbon atoms, aromatic vinyl compounds, norbornenes, cyclopentadiene, dicyclopentadiene,
Examples thereof include vinylsilanes. These may be used alone or in combination of two or more.

The isobutylene polymer has a number average molecular weight of 500 to 200,000. Number average molecular weight of 50
When it is less than 0, predetermined physical properties are not expressed and 200,000
When it exceeds, the isobutylene polymer becomes solid,
It is limited to the above range. Preferably 1000-1000
00, more preferably 3000 to 50000.

The plasticizer used in the present invention is not particularly limited as long as it has good compatibility with the isobutylene polymer, has a relatively high boiling point, and does not inhibit the hydrosilylation reaction. For example, when the main chain skeleton of the isobutylene-based polymer is a saturated hydrocarbon such as polyisobutylene, examples thereof include polybutene, hydrogenated polybutene, α-methylstyrene oligomer, biphenyl, and triphenyl. Hydrocarbon compounds such as phenyl, triaryldimethane, alkylenetriphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyldiphenyl; BAA-15 (manufactured by Daihachi Chemical Co., Ltd.), P
-103 (manufactured by Dainippon Ink Co., Ltd.), W320 (manufactured by Dainippon Ink Co., Ltd.), PN-150 (manufactured by ADEKA ARGUS CORPORATION) and the like adipic acid ester compounds; Manufactured by K.K.), W-700 (manufactured by Dainippon Ink and Chemicals, Inc.) and the like;
NS-100, NM-26, NP-24, PS-32,
Petroleum-based process oils such as PW-32 and PX-32 (manufactured by Idemitsu Kosan Co., Ltd.); Alken-68 (manufactured by Nippon Petroleum Detergent Co.);
BF-1000 (manufactured by ADEKA ARGUS CORPORATION); KE-828
(Manufactured by Arakawa Chemical Co., Ltd.); DOTP (manufactured by New Japan Rika Co., Ltd.) and the like can be mentioned, but the invention is not necessarily limited thereto. Of these, Alken-68, PS-3
2, PW-32, PX-32, DOTP, NS-10
0 and TOTM are preferable because the loss on heating is small.

The plasticizer has a number average molecular weight of 100 to 1
It is preferably 000. Number average molecular weight is 1
If it is less than 00, the boiling point of the plasticizer becomes low and 1000
When it exceeds, the viscosity becomes high and it becomes difficult to handle. It is more preferably 200 to 800.

The above-mentioned plasticizer has a paraffin content of 50 to 90% and a naphthene content of 5 as determined by the nd-M method.
It is preferably 0 to 10%. In the present specification, "n-
The “d-M method” refers to obtaining the paraffin content and the naphthene content by substituting the values of the refractive index n, the density d, and the molecular weight M into the empirical formula of the nd-M method (petroleum hydrocarbon chemistry. , Volume 2, written by Kiyoshi Ikebe et al., Kyoritsu Shuppan). When the paraffin content and the naphthene content are out of the above ranges, oxidative deterioration of the plasticizer is likely to occur. More preferably a paraffin content of 60
-80% and naphthene content 40-20%.

Further, the plasticizer preferably has an aromatic content of 1% or less as determined by ring analysis. In the present specification, the “ring analysis” means measuring the relative refraction r ²⁰ _D and the molecular weight M of the plasticizer, obtaining the aniline point corresponding to the measured molecular weight M and the relative refraction r ²⁰ _D , and measuring the aniline point and the measured aniline point. The difference from the aniline point [AP] is calculated, and based on the result, the aroma content is calculated by the following formula: aroma content (%) = 0.68 × [AP] in the plasticizer (petroleum hydrocarbon chemistry , Volume 2, written by Kiyoshi Ikebe et al., Kyoritsu Shuppan). Aroma content is 1%
If it exceeds, the weather resistance of the product is lowered and the stability is lowered. It is more preferably 0.1% or less.

The amount of the plasticizer used can be appropriately determined in consideration of the effect of lowering the viscosity of the isobutylene polymer and the intended use of the isobutylene polymer having a functional group. Isobutylene polymer 100
It can be 10 to 100 parts by weight with respect to parts by weight.

The compound represented by the above general formula (I) used in the present invention is a hydrosilyl group-containing compound. Specific examples of the compound represented by the general formula (I) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and trimethylsiloxydichlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethyl. Silane, methoxydimethylsilane, dimethoxyphenylsilane, 1,3,3
Alkoxysilanes such as 5,5,7,7-heptamethyl-1,1-dimethoxytetrasiloxane; Acyloxysilanes such as methyldiacetoxysilane and trimethylsiloxymethylacetoxysilane; Dimethylsilane, trimethylsiloxymethylsilane, 1, Hydrosilanes having two or more Si-H bonds in the molecule such as 1,3,3-tetramethyldisiloxane and 1,3,5-trimethylcyclotrisiloxane; methyldi (isopropenyloxy)
Examples thereof include alkenyloxysilanes such as silane.

Of these compounds, chlorosilanes such as trichlorosilane and methyldichlorosilane are preferable because they have high hydrosilylation activity. Further, alkoxysilanes such as trimethoxysilane and dimethoxymethylsilane are preferable because the resulting isobutylene-based polymer having a functional group has a mild hydrolyzability. Furthermore, hydrosilanes having two or more Si-H bonds in the molecule increase the molecular weight of the resulting isobutylene-based polymer having a functional group by 2 times, 3 times, etc. depending on the amount used. Is preferable and the range of molecular weight control can be expanded, which is preferable.

The amount of the compound represented by the general formula (I) added is preferably 0.2 to 20 mol per 1 mol of the alkenyl group in the isobutylene polymer. From the viewpoint of economic efficiency in industrial operations, 0.5 to 10 mol is more preferable, and 0.8 to 3 mol is still more preferable.

The platinum catalyst used in the present invention is not particularly limited, and examples thereof include simple substance of platinum, platinum metal supported on a carrier, platinum compound, platinum complex and the like. Examples of such substances include platinum metal supported on a carrier such as alumina, silica, carbon black; chloroplatinic acid; platinum compounds such as complexes of chloroplatinic acid with alcohols, aldehydes, ketones; Pt ( CH ₂ =
CH) ₂ [P (C ₆ H ₅ ) ₃ ], Pt (CH ₂ = CH)
Platinum-olefin complex such as ₂ Cl ₂ ; Pt [(CH ₂ =
CH) (CH ₃ ) ₂ SiOSi (CH ₃ ) ₂ (CH ₂ =
CH)], Pt [(CH ₃ ) (CH ₂ = CH) SiO]
Platinum-vinyl siloxane complex such as ₄ ; Pt [P (C ₆ H
_{5) 3] 4,} Pt [P (C ₄ H _{9) 3] 4,} such as platinum - phosphine _{complex; Pt [P (C 6 H} 5 O) 3] 4 and the like of platinum - phosphite complex; platinum - acetylacetonate A nato complex etc. can be mentioned. Also, dicarbonyldichloroplatinum, platinum-hydrocarbon complexes described in US Pat. No. 3,159,601 and US Pat. No. 3,159,662, platinum-described in US Pat. No. 3,220,972. It is also possible to use an alcoholate catalyst or the like. Further, it may be a platinum chloride-olefin composite described in US Pat. No. 3,516,946. Of these, chloroplatinic acid, a platinum-olefin complex, a platinum-acetylacetonate complex, and a platinum-vinylsiloxane complex are preferable from the viewpoint of reaction activity. In the present invention, these catalysts may be used alone,
Two or more kinds may be used in combination.

The amount of the platinum catalyst catalyst added is 1 with respect to 1 mol of the alkenyl group in the isobutylene polymer.
^0-8 to ^10-1 mol is preferred. When it is less than 10 ^-8 mol, the hydrosilylation reaction does not proceed sufficiently, and when it exceeds 10 ^-1 mol, disadvantages such as uneconomical, corrosive and by-product formation increase. More preferably, it is 10 ⁻⁶ to 10 ⁻³ mol.

In the present invention, the platinum catalyst catalyst is preferably used by diluting it with an inert solvent for easy handling and stabilization. As the solvent, for example, hydrocarbon solvents such as benzene, toluene and xylene; various alcohols; glycols; polar solvents such as esters are preferable.

In the present invention, as described in detail above, after the isobutylene polymer is mixed with the plasticizer in an inert gas atmosphere, the isobutylene polymer and the compound represented by the general formula (I) are mixed. React with. The above-mentioned reaction can be carried out in an air phase or in an atmosphere of oxygen concentration adjusted to a desired concentration with an inert gas, as usual. In this case, the reaction temperature of the above reaction can be appropriately set depending on the catalyst concentration, the nature of the reaction substance, etc., but is generally preferably in the range of 30 to 200 ° C. More preferably, it is in the range of 50 to 120 ° C.
Further, the pressure can be similarly set as appropriate, but in general, 1 to
50 kg / cm ² G is preferable, and more preferably 0 to
20 kg / cm ² G, more preferably 0 to 10
kg / cm ² G.

[0033]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 100 g of a plasticizer (PS-32, manufactured by Idemitsu Kosan Co., Ltd.) was placed in a 300 mL three-necked flask, the flask was replaced with nitrogen, and then heated at 140 ° C. for 1 hour, and 20 g of PS-32 was taken out. It was Next, in another 300 mL three-necked flask, 20.58 g of the terminal vinyl group-containing isobutylene polymer and 10.3 g of the PS-32 taken out (50 parts with respect to the isobutylene polymer) were added, and a nitrogen atmosphere was added. The mixture was stirred at about 75 ° C. and mixed well. After that, the gas phase part was replaced with air, and dimethoxymethylsilane (DMS) 0.66 was added thereto.
g (1. with respect to the terminal vinyl group of the isobutylene polymer.
5 equivalents), and 1 × 10 ⁻⁴ equivalents (49.6 μL) of Pt-vinylsiloxane catalyst to the terminal vinyl groups.
In addition, the hydrosilylation reaction was started. The reaction conversion rate of the silylation reaction after a certain reaction time was determined by the following method. The results are shown by □ in FIG. Further, the carbonyl product concentration after a certain reaction time was determined by the following method. The results are shown by □ in FIG.

Evaluation method 1. Reaction conversion rate (X) The olefin absorption of the terminal vinyl group-containing isobutylene-based polymer was measured by FT-IR (DR-8000, manufactured by Shimadzu Corporation) analysis, converted into an area, and calculated by the following formula. X = 1-S _t / S ₀ S ₀ : vinyl peak area value before reaction S _t : vinyl peak area value at reaction time t Carbonyl product concentration n-caprinaldehyde having 10 carbon atoms was dissolved as a long-chain carbonyl compound in a plasticizer, and carbonyl absorption was IR-measured at different concentrations. The peak area value (S _CO ) of the carbonyl absorption and the carbonyl concentration ( C _CO ), and the following relational expression was obtained. C _CO (× 10 ^-2 mmol / g) = 0.437 + 0.06
29 × S _CO The carbonyl product concentration in the hydrosilylation reaction system was determined using the above relational expression.

Example 2 100 g of a plasticizer (PS-32, manufactured by Idemitsu Kosan Co., Ltd.) was placed in a 300 mL three-necked flask, the flask was replaced with nitrogen, and then heated at 140 ° C. for 4 hours to take out 20 g of PS-32. It was Next, in another 300 mL three-necked flask, 22.68 g of the terminal vinyl group-containing isobutylene-based polymer and 11.4 g (50 parts with respect to the isobutylene-based polymer) of the PS-32 taken out were added, and a nitrogen atmosphere was added. The mixture was stirred at about 75 ° C. and mixed well. After that, the gas phase part was replaced with air, and dimethoxymethylsilane (DMS) 0.72 was added thereto.
g (1. with respect to the terminal vinyl group of the isobutylene polymer.
5 equivalents), and 1 × 10 ⁻⁴ equivalents (54.7 μL) of Pt-vinylsiloxane catalyst to the terminal vinyl groups.
In addition, the hydrosilylation reaction was performed in the same manner as in Example 1 to determine the reaction conversion rate and the carbonyl product concentration. The results are shown in FIGS. 1 and 3 by ⋄.

Example 3 100 g of a plasticizer (PS-32, manufactured by Idemitsu Kosan Co., Ltd.) was placed in a 300 mL three-necked flask, the flask was replaced with nitrogen, and then heated at 140 ° C. for 8 hours, and 20 g of PS-32 was taken out. It was Next, 17.11 g of the terminal vinyl group-containing isobutylene-based polymer and 8.5 g (50 parts with respect to the isobutylene-based polymer) of the PS-32 taken out were added to another 300 mL three-necked flask, and a nitrogen atmosphere was added. The mixture was agitated at about 75 ° C. and thoroughly mixed. After that, the gas phase part was replaced with air, and dimethoxymethylsilane (DMS) 0.55 was added thereto.
g (1. with respect to the terminal vinyl group of the isobutylene polymer.
5 equivalents), and 1 × 10 ⁻⁴ equivalents (41.2 μL) of Pt-vinylsiloxane catalyst to the terminal vinyl groups.
In addition, the hydrosilylation reaction was performed in the same manner as in Example 1 to determine the reaction conversion rate and the carbonyl product concentration. The results are shown by X marks in FIGS. 1 and 3.

Example 4 100 g of a plasticizer (PW-32, manufactured by Idemitsu Kosan Co., Ltd.) was placed in a 300 mL three-necked flask, the flask was purged with nitrogen, and then heated at 140 ° C. for 1 hour, and 20 g of PW-32 was taken out. It was Next, in another 300 mL three-necked flask, 20.26 g of the terminal vinyl group-containing isobutylene polymer and 10.3 g of the PW-32 taken out (50 parts with respect to the isobutylene polymer) were added, and a nitrogen atmosphere was added. The mixture was stirred at about 75 ° C. and mixed well. Then, the gas phase part was replaced with air, and dimethoxymethylsilane (DMS) 0.65 was added thereto.
g (1. with respect to the terminal vinyl group of the isobutylene polymer.
5 equivalents), and 1 × 10 ⁻⁴ equivalents (48.8 μL) of Pt-vinylsiloxane catalyst to the terminal vinyl groups.
In addition, the hydrosilylation reaction was performed in the same manner as in Example 1 to determine the reaction conversion rate and the carbonyl product concentration. The results are shown by + marks in FIGS. 1 and 3, respectively.

Example 5 100 g of a plasticizer (PW-32, manufactured by Idemitsu Kosan Co., Ltd.) was placed in a 300 mL three-necked flask, and the flask was replaced with nitrogen, and then heated at 140 ° C. for 4 hours, and 20 g of PW-32 was taken out. It was Next, to another 300 mL three-necked flask, 20.03 g of the terminal vinyl group-containing isobutylene polymer and 10.0 g of the PW-32 taken out (50 parts with respect to the isobutylene polymer) were added, and a nitrogen atmosphere was added. The mixture was agitated at about 75 ° C. and thoroughly mixed. After that, the gas phase part was replaced with air, and dimethoxymethylsilane (DMS) 0.64 was added thereto.
g (1. with respect to the terminal vinyl group of the isobutylene polymer.
5 equivalents), and 1 × 10 ⁻⁴ equivalents (48.3 μL) of Pt-vinylsiloxane catalyst to the terminal vinyl groups.
In addition, the hydrosilylation reaction was performed in the same manner as in Example 1 to determine the reaction conversion rate and the carbonyl product concentration. The results are shown by circles in FIGS. 2 and 4, respectively.

Example 6 100 g of a plasticizer (PW-32, manufactured by Idemitsu Kosan Co., Ltd.) was placed in a 300 mL three-necked flask, and the flask was replaced with nitrogen, and then heated at 140 ° C. for 8.5 hours to obtain PW-32. 20 g
I took it out. Next, in another 300 mL three-necked flask, 22.61 g of the terminal vinyl group-containing isobutylene-based polymer was added.
Then, 11.3 g (50 parts with respect to the isobutylene polymer) of the PW-32 taken out was added, and the mixture was placed in a nitrogen atmosphere at 75%.
Stir at around 0 ° C. and mix well. Then, the gas phase part was replaced with air, and dimethoxymethylsilane (DMS) was added thereto.
72 g (1.5 equivalents to the terminal vinyl group of the isobutylene polymer) was added, and 1 × 10 ⁻⁴ equivalent (54.5 μm) of Pt-vinylsiloxane catalyst was added to the terminal vinyl group.
L) In addition, a hydrosilylation reaction was carried out in the same manner as in Example 1 to determine the reaction conversion rate and the carbonyl product concentration. The results are shown by □ marks in FIGS. 2 and 4, respectively.

Example 7 100 g of a plasticizer (PS-32, manufactured by Idemitsu Kosan Co., Ltd.) was placed in a 300 mL three-necked flask, and the flask was replaced with nitrogen, and then heated at 90 ° C. for 2 hours to take out 20 g of PS-32. It was Next, in another 300 mL three-necked flask, 26.73 g of the terminal vinyl group-containing isobutylene polymer and 13.4 g (50 parts with respect to the isobutylene polymer) of the PS-32 taken out were added, and a nitrogen atmosphere was added. The mixture was stirred at about 75 ° C. and mixed well. After that, the gas phase is replaced with air,
Dimethoxymethylsilane (DMS) 0.85g
(1.5 with respect to the terminal vinyl group of the isobutylene-based polymer
Equivalent amount), and 1 × 10 ⁻⁴ equivalent (64.4 μL) of Pt-vinylsiloxane catalyst to the terminal vinyl group was added to carry out the hydrosilylation reaction in the same manner as in Example 1.
The reaction conversion rate and carbonyl product concentration were determined. The results are shown in FIG. 2 and FIG.

Example 8 100 g of a plasticizer (PS-32, manufactured by Idemitsu Kosan Co., Ltd.) was placed in a 300 mL three-necked flask, the flask was replaced with nitrogen, and then heated at 90 ° C. for 4 hours to take out 20 g of PS-32. It was Next, in another 300 mL three-necked flask, 26.80 g of the terminal vinyl group-containing isobutylene polymer and 13.4 g of the above-mentioned PS-32 (50 parts relative to the isobutylene polymer) were added, and a nitrogen atmosphere was added. The mixture was stirred at about 75 ° C. and mixed well. After that, the gas phase is replaced with air,
Dimethoxymethylsilane (DMS) 0.85g
(1.5 with respect to the terminal vinyl group of the isobutylene-based polymer
Equivalent amount), and 1 × 10 ⁻⁴ equivalent (64.4 μL) of Pt-vinylsiloxane catalyst to the terminal vinyl group was added to carry out the hydrosilylation reaction in the same manner as in Example 1.
The reaction conversion rate and carbonyl product concentration were determined. The results are shown by X marks in FIGS. 2 and 4, respectively.

Comparative Example 1 In a 500 mL separable flask, 120 g of an isobutylene-based polymer containing a terminal vinyl group and 36 g of a plasticizer (PS-32, manufactured by Idemitsu Kosan Co., Ltd.) (5 with respect to the isobutylene-based polymer) were used.
(0 part) was added, and the mixture was stirred at about 75 ° C. and thoroughly mixed.
This was heat-treated in an air atmosphere at 140 ° C. for 4 hours, and then dimethoxymethylsilane (DMS) 4.44 was added thereto.
ml (1.5 equivalents to the terminal vinyl group of the isobutylene polymer) was added, and a Pt-vinylsiloxane catalyst (10-fold diluted xylene solution 8.31 × 10 ⁻⁶ mmol / μL) was added.
Is equivalent to 1 × 10 ⁻⁴ equivalent (288.8μ
L) was added to start the hydrosilylation reaction. This reaction was carried out by substituting the gas phase portion with air before the reaction. The reaction conversion rate of the silylation reaction and the carbonyl product concentration after a certain reaction time were determined in the same manner as in Example 1. Each result is ○
It is shown in FIG. 1 and FIG. 3 by the mark.

[0044]

According to the present invention, prior to carrying out the hydrosilylation reaction of the isobutylene polymer in the plasticizer system, the hydrosilylation reaction can be performed by mixing the plasticizer and the isobutylene polymer in an inert gas atmosphere. It is possible to suppress the production of a carbonyl compound that is a reaction inhibitor before the initiation of the chemical reaction. For this reason, the hydrosilylation reaction can be stably initiated and the reaction can be stably proceeded, so that an isobutylene polymer having a functional group can be produced with high productivity and high quality. it can.

[Brief description of drawings]

FIG. 1 is a diagram showing the reaction conversion rates of Examples 1 to 4 and Comparative Example 1. The vertical axis represents the reaction conversion rate, and the horizontal axis represents the reaction time (minutes).

FIG. 2 is a diagram showing the reaction conversion rates of Examples 5 to 8. The vertical axis is
The reaction conversion rate is shown, and the horizontal axis shows the reaction time (minutes).

FIG. 3 is a graph showing carbonyl product concentrations in Examples 1 to 4 and Comparative Example 1. The vertical axis is the carbonyl product concentration (× 10 ^-2
mmol / g) and the horizontal axis represents the reaction time (minutes).

FIG. 4 is a diagram showing carbonyl product concentrations in Examples 5 to 8. The vertical axis represents the concentration of carbonyl products (× 10 ^-2 mmol
/ G), and the horizontal axis represents the reaction time (minutes).

Claims (5)

[Claims] 1. An isobutylene-based polymer containing at least one terminal alkenyl group and having a number average molecular weight of 500 to 200,000 is mixed with a plasticizer in an inert gas atmosphere, and then a platinum catalyst is used. Formula (I): (In the formula, R ¹ and R ² are the same or different and are an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
Alternatively, a (R ′) ₃ SiO— group (wherein R ′ is a carbon number 1
To 20 monovalent hydrocarbon groups or hydrogen). X
Represents a hydroxyl group, a halogen, an alkoxyl group or an acyloxyl group, and when two or more are bonded, they may be the same or different. a is 0 to 3
Represents an integer. b represents an integer of 0 to 2. m is 0
Represents an integer of 18. ) A method for producing an isobutylene-based polymer having a functional group, which comprises reacting with a compound represented by 2. The inert gas atmosphere has an oxygen concentration of 0.01.
% Or less, The method for producing an isobutylene polymer having a functional group according to claim 1. 3. The number average molecular weight of the plasticizer is 100 to 100.
The method for producing an isobutylene-based polymer having a functional group according to claim 1 or 2, wherein the paraffin-based plasticizer is 0. 4. The plasticizer has a composition of 50 to 90% paraffin and a naphthene of 50 to 10 as determined by the ndM method.
%, And the aroma content determined by ring analysis is 1
% Or less, the method for producing an isobutylene-based polymer having a functional group according to claim 1, 2 or 3. 5. The mixing of the isobutylene polymer and the plasticizer is performed at 10 to 300 ° C. 1, 2, 3 or 4.
A method for producing an isobutylene-based polymer having a functional group as described.