JP2015124274A - Production method of polyether rubber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method which enables a polyether rubber having a group containing cationic nitrogen-containing aromatic heterocyclic ring, to be obtained with high productivity.SOLUTION: There is provided the production method of polyether rubber containing a unit represented by formula (1) in an amount of 0.1 to 30 mol%. In the production method, a polyether rubber containing epihalohydrin monomer unit in an amount of 0.1 mol% or more and a nitrogen atom-containing aromatic heterocyclic compound such as imidazole are reacted in a solution under the presence of alkali metal halogenide and/or alkali earth metal halogenide, so that at least a portion of the halogen atoms constituting the epihalohydrin monomer unit is substituted to a group containing cationic nitrogen-containing aromatic heterocyclic ring.

Description

  The present invention relates to a method for producing a polyether rubber, and more specifically to a method for producing a polyether rubber having a group containing a cationic nitrogen-containing aromatic heterocycle. The present invention also relates to a polyether rubber obtained by such a method for producing a polyether rubber, and a crosslinkable rubber composition and a rubber cross-linked product using the polyether rubber.

  In image forming apparatuses such as printers, electrophotographic copying machines, and facsimile machines, conductive members such as conductive rolls, conductive blades, and conductive belts are used as mechanisms that require semiconductivity. .

  Such a conductive member has a desired range of conductivity (electric resistance value and its variation, environmental dependency, voltage dependency), non-contamination, low hardness, dimensional stability, etc., depending on the application. Various performances are required.

  As rubber constituting a part of such a conductive member, polyether rubber having semiconductivity in the rubber itself has been used. However, in recent years, image forming apparatuses have been required to increase the speed, and further reduction in electrical resistance has been desired for conductive members, particularly conductive rolls.

  In addition, conventionally, when a voltage is applied to a conductive member in which polyether rubber or the like is used, the conductive member is energized and deteriorated by continuous use, thereby increasing the electrical resistance value of the conductive member, When used for an image forming apparatus, there is a problem that the image quality deteriorates. For such a problem, for example, in Patent Document 1, a monomer having an onium ion introduced into a polyether rubber using a nitrogen atom-containing aromatic heterocyclic compound such as 1-methylimidazole as an onium agent. A technique in which a body unit is contained in an amount of 0.1 mol% or more and less than 30 mol% is disclosed.

JP 2012-107230 A

  In Patent Document 1, a monomer unit having an onium ion in a polyether rubber is obtained by reacting the polyether rubber with an onium forming agent comprising a nitrogen atom-containing aromatic heterocyclic compound such as 1-methylimidazole. Thus, the conductivity can be improved. However, in the technique of Patent Document 1, the reaction between the polyether rubber and the onium agent is performed by kneading them without using a solvent. For example, in a solution using a solvent, Compared with the case of performing the reaction, it is not easy to remove the unreacted onium reagent. However, when the reaction is performed in a solution using a solvent, the reaction rate is slow and the productivity is inferior. Therefore, improvement in productivity has been desired.

  The present invention has been made in view of such a situation, and a polyether rubber having a group containing a cationic nitrogen-containing aromatic heterocycle can be obtained with high productivity. It aims at providing the manufacturing method of ether rubber. Another object of the present invention is to provide a polyether rubber obtained by such a method for producing a polyether rubber, and a crosslinkable rubber composition and a rubber cross-linked product using the polyether rubber.

  The present inventors conducted extensive studies to achieve the above object. As a result, the reaction between polyether rubber and an onium-containing agent composed of a nitrogen atom-containing aromatic heterocyclic compound such as 1-methylimidazole (onium) It is found that the reaction rate can be improved by performing the reaction in the presence of an alkali metal halide and / or an alkaline earth metal halide when the reaction is carried out in solution. It came to complete.

（上記一般式（１）中、Ａ^＋は、カチオン性含窒素芳香族複素環を含有する基である。前記カチオン性含窒素芳香族複素環を含有する基は、該カチオン性含窒素芳香族複素環を構成する窒素原子の１つを介して、上記一般式（１）に示す「２」の位置の炭素原子と結合している。Ｘ⁻は任意の対アニオンである。） That is, according to the present invention, there is provided a method for producing a polyether rubber containing a unit represented by the following general formula (1) in an amount of 0.1 mol% or more and less than 30 mol%, wherein an epihalohydrin monomer unit is Reaction of polyether rubber containing 0.1 mol% or more with nitrogen atom-containing aromatic heterocyclic compound in solution in the presence of alkali metal halide and / or alkaline earth metal halide To provide a method for producing a polyether rubber, wherein at least a part of halogen atoms constituting the epihalohydrin monomer unit is substituted with a group containing a cationic nitrogen-containing aromatic heterocyclic ring. The

(In the above general formula (1), A ⁺ is a group containing a cationic nitrogen-containing aromatic heterocycle. The group containing the cationic nitrogen-containing aromatic heterocycle is the cationic nitrogen-containing aromatic heterocycle. It is bonded to the carbon atom at the position “2” shown in the general formula (1) through one of the nitrogen atoms constituting the heterocyclic ring. X ⁻ is an arbitrary counter anion.)

  In the method for producing a polyether rubber according to the present invention, the alkali metal halide and / or alkaline earth metal halide is preferably an alkali metal iodide.

  Further, according to the present invention, the polyether rubber obtained by the above production method, the crosslinkable rubber composition obtained by blending the polyether rubber with a crosslinking agent, and the rubber obtained by crosslinking the crosslinkable rubber composition A cross-linked product is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the polyether rubber which can obtain the polyether rubber which has group containing a cationic nitrogen-containing aromatic heterocyclic ring with high productivity can be provided. Moreover, according to this invention, the polyether rubber obtained by such a manufacturing method, the crosslinkable rubber composition and rubber | gum crosslinked material using this polyether rubber can also be provided.

（上記一般式（１）中、Ａ^＋は、カチオン性含窒素芳香族複素環を含有する基である。前記カチオン性含窒素芳香族複素環を含有する基は、該カチオン性含窒素芳香族複素環を構成する窒素原子の１つを介して、上記一般式（１）に示す「２」の位置の炭素原子と結合している。Ｘ⁻は任意の対アニオンである。）
なお、以下において、「カチオン性含窒素芳香族複素環を含有する基」を、「オニウムイオン含有基」と記す場合がある。 <Method for producing polyether rubber>
The method for producing a polyether rubber of the present invention is a method for producing a polyether rubber containing a unit represented by the following general formula (1) in an amount of 0.1 mol% or more and less than 30 mol%, and an epihalohydrin monomer A polyether rubber containing 0.1 mol% or more of a unit and a nitrogen atom-containing aromatic heterocyclic compound in a solution in the presence of an alkali metal halide and / or an alkaline earth metal halide. In the reaction, at least a part of the halogen atoms constituting the epihalohydrin monomer unit is substituted with a group containing a cationic nitrogen-containing aromatic heterocycle.

(In the above general formula (1), A ⁺ is a group containing a cationic nitrogen-containing aromatic heterocycle. The group containing the cationic nitrogen-containing aromatic heterocycle is the cationic nitrogen-containing aromatic heterocycle. It is bonded to the carbon atom at the position “2” shown in the general formula (1) through one of the nitrogen atoms constituting the heterocyclic ring. X ⁻ is an arbitrary counter anion.)
Hereinafter, the “group containing a cationic nitrogen-containing aromatic heterocycle” may be referred to as an “onium ion-containing group”.

  The polyether rubber containing 0.1 mol% or more of epihalohydrin monomer unit used in the present invention can be obtained by ring-opening polymerization of the epihalohydrin monomer by a solution polymerization method or a solvent slurry polymerization method. As will be described later, the polyether rubber containing 0.1 mol% or more of the epihalohydrin monomer unit used in the present invention contains an ethylene oxide monomer and an unsaturated oxide monomer in addition to the epihalohydrin monomer. A copolymer obtained by ring-opening polymerization is preferred. However, it is necessary that the epihalohydrin monomer is subjected to copolymerization by 0.1 mol% or more.

  The epihalohydrin monomer constituting the epihalohydrin monomer unit is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, epiiodohydrin, epifluorohydrin, and the like. Epichlorohydrin is preferred. An epihalohydrin monomer may be used individually by 1 type, and may use 2 or more types together.

  The polymerization catalyst used for ring-opening polymerization of the epihalohydrin monomer is not particularly limited as long as it is a general polyether polymerization catalyst. As a polymerization catalyst, for example, a catalyst obtained by reacting water and acetylacetone with organoaluminum (Japanese Patent Publication No. 35-15797); a catalyst obtained by reacting phosphoric acid and triethylamine with triisobutylaluminum (Japanese Patent Publication No. 46-27534) Catalyst obtained by reacting diazabiacycloundecene organic acid salt and phosphoric acid with triisobutylaluminum (Japanese Examined Patent Publication No. 56-51171); Catalyst comprising aluminum alkoxide partial hydrolyzate and organozinc compound (Japanese Examined Patent Publication No. 43-2945); a catalyst comprising an organic zinc compound and a polyhydric alcohol (Japanese Examined Patent Publication No. 45-7751); a catalyst comprising a dialkylzinc and water (Japanese Examined Patent Publication No. 36-3394); tributyl A catalyst comprising tin chloride and tributyl phosphate (Patent No. 322397) JP); and the like.

  The polymerization solvent is not particularly limited as long as it is an inert solvent. For example, aromatic hydrocarbons such as benzene and toluene; linear saturated hydrocarbons such as n-pentane and n-hexane; cyclopentane, And cyclic saturated hydrocarbons such as cyclohexane; Among these, in the case of ring-opening polymerization by a solution polymerization method, it is preferable to use an aromatic hydrocarbon, more preferably toluene, from the viewpoint of the solubility of the polyether rubber.

  The polymerization reaction temperature is preferably 20 to 150 ° C, more preferably 40 to 130 ° C. The polymerization mode can be carried out by any method such as batch system, semi-batch system, and continuous system.

  The polyether rubber containing the epihalohydrin monomer unit in an amount of 0.1 mol% or more may be any copolymer type of block copolymer or random copolymer, but is preferably a random copolymer.

  The method for recovering the polyether rubber containing the epihalohydrin monomer unit in an amount of 0.1 mol% or more from the solvent is not particularly limited. For example, the method is performed by appropriately combining coagulation, filtration, and drying methods. As a method for coagulating the polyether rubber from the solvent in which the polyether rubber is dissolved, for example, a conventional method such as steam stripping or a precipitation method using a poor solvent can be used. In addition, as a method of filtering the polyether rubber from the slurry containing the polyether rubber, a method using a sieve such as a rotary screen or a vibrating screen; a centrifugal dehydrator; Can do. Furthermore, as a method for drying the polyether rubber, for example, a method of dehydrating using a compressed water squeezing machine such as a roll, a Banbury dehydrator, a screw extruder dehydrator; a screw type extruder, a kneader type dryer, Examples include a method using a dryer such as an expander dryer, a hot air dryer, and a vacuum dryer. These compressed water squeezers and dryers are used singly or in combination of two or more.

  In the production method of the present invention, a polyether rubber containing 0.1 mol% or more of such an epihalohydrin monomer unit and a nitrogen atom-containing aromatic heterocyclic compound are converted into an alkali metal halide described later. And / or by reacting in solution in the presence of an alkaline earth metal halide, at least a part of the halogen atoms constituting the epihalohydrin monomer unit contains a cationic nitrogen-containing aromatic heterocycle The structural unit represented by the general formula (1) is introduced into the polyether rubber by substituting it with the group to be used.

  In the present invention, a reaction between a polyether rubber containing an epihalohydrin monomer unit of 0.1 mol% or more and a nitrogen atom-containing aromatic heterocyclic compound is carried out in a solution. Alkali metal halides and / or alkaline earth metal halides are used, and epihalohydrin monomer units are reduced to 0 by the action of such alkali metal halides and / or alkaline earth metal halides. The reaction rate of the polyether rubber containing 1 mol% or more and the nitrogen atom-containing aromatic heterocyclic compound can be improved, whereby the above general formula (1) can be obtained with high productivity. A polyether rubber containing a unit represented by the formula: 0.1 mol% or more and less than 30 mol% can be produced. Moreover, according to this invention, since it reacts in a solution, an unreacted nitrogen atom containing aromatic heterocyclic compound can be removed easily.

  The nitrogen atom-containing aromatic heterocyclic compound used in the present invention (hereinafter sometimes referred to as “onium agent”) is not particularly limited as long as it is an aromatic heterocyclic compound containing a nitrogen atom, For example, 5-membered heterocyclic compounds such as imidazole, 1-methylimidazole, pyrrole, 1-methylpyrrole, thiazole, oxazole, pyrazole, isoxazole; pyridine, pyrazine, pyrimidine, pyridazine, triazine, 2,6-lutidine, etc. 6-membered heterocyclic compounds; condensed heterocyclic compounds such as quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, purine, indole, isoindole, benzimidazole, benzoxazole, and benzisoxazole; Among these, a 5-membered heterocyclic compound and a 6-membered heterocyclic compound are preferable, and 1-methylimidazole is more preferable from the viewpoint of substance stability after the reaction.

  Although the amount of the onium agent used is not particularly limited, it depends on the structure of the onium agent used or the polyether rubber, the substitution rate of the onium ion-containing group in the target polyether rubber, etc. What is necessary is just to determine in the range from which the content rate of the unit represented becomes 0.1 mol% or more and less than 30 mol%. Specifically, the amount of the oniumizing agent used is usually 0.01 to 100 mol, preferably 0.02 to 50 mol, relative to 1 mol of the halogen atom constituting the epihalohydrin monomer unit of the polyether rubber to be used. More preferably, it is 0.02-10 mol, More preferably, it is the range of 0.02-2 mol. If the amount of the onium agent is too small, the substitution reaction is slow, and there is a possibility that a polyether rubber having an onium ion-containing group having a desired composition (hereinafter also referred to as “cationized polyether rubber”) cannot be obtained. On the other hand, if the amount of the onium agent is too large, it may be difficult to remove the unreacted onium agent from the obtained cationized polyether rubber.

The alkali metal halide and / or alkaline earth metal halide used in the present invention is not particularly limited, but chlorides such as sodium chloride, potassium chloride, magnesium chloride, calcium chloride, barium chloride; sodium iodide, And iodide such as potassium iodide, magnesium iodide, calcium iodide and barium iodide; bromides such as sodium bromide, potassium bromide, magnesium bromide, calcium bromide and barium bromide; Among these, when the polyether rubber containing an epihalohydrin monomer unit is reacted with an onium agent in a solution, the reactivity can be further increased, thereby further increasing the reaction rate. Alkali metal iodide is preferable, and sodium iodide is more preferable.
In addition, the alkali metal halide and / or the alkaline earth metal halide can be used singly or in combination of two or more.

  The amount of alkali metal halide and / or alkaline earth metal halide used is not particularly limited, but may be selected according to the type of alkali metal halide and / or alkaline earth metal halide used. Preferably, it is preferably 0.001 to 1 mol, more preferably 0.001 to 0.1 mol, and still more preferably 0.002 to 1 mol of the halogen atom constituting the epihalohydrin monomer unit of the polyether rubber to be used. The range is -0.05 mol. If the amount of alkali metal halide and / or alkaline earth metal halide used is too small, the effect of addition, that is, the polyether rubber containing the epihalohydrin monomer unit and the oniumizing agent in solution. When making it react, there exists a possibility that the improvement effect of the reactivity may become difficult to obtain. On the other hand, if the amount of alkali metal halide and / or alkaline earth metal halide used is too large, it may be difficult to remove.

In addition, as a solvent used for the reaction between the polyether rubber containing an epihalohydrin monomer unit and the onium agent, an inert solvent is preferably used, and even a nonpolar solvent is a polar solvent. May be. Examples of the nonpolar solvent include aromatic hydrocarbons such as benzene and toluene; chain saturated hydrocarbons such as n-pentane and n-hexane; alicyclic saturated hydrocarbons such as cyclopentane and cyclohexane; It is done. Examples of polar solvents include ethers such as tetrahydrofuran, anisole and diethyl ether; esters such as ethyl acetate and ethyl benzoate; ketones such as acetone, 2-butanone and acetophenone; aprotic polar solvents such as acetonitrile, dimethylformamide and dimethyl sulfoxide Protic polar solvents such as ethanol, methanol, water; and the like. In addition, a solvent can be used individually by 1 type or in combination of 2 or more types.
Although the usage-amount of a solvent is not specifically limited, Preferably it is 100-5000 weight part with respect to 100 weight part of polyether rubber to be used, More preferably, it is 200-2000 weight part, Especially preferably, it is 500-1500 weight part.

  In the present invention, a polyether rubber containing 0.1 mol% or more of an epihalohydrin monomer unit and an onium agent are present in the presence of an alkali metal halide and / or an alkaline earth metal halide, The mixing order and mixing method for mixing these in a solution and reacting them are not particularly limited, and examples thereof include the following methods. That is, a method in which an onium-containing agent and an alkali metal halide and / or an alkaline-earth metal halide are added and mixed in a solution obtained by dissolving polyether rubber in a solvent, and the onium agent is dissolved in a solvent. A method in which polyether rubber and alkali metal halide and / or alkaline earth metal halide are added to and mixed with the solution, and both polyether rubber and onium agent are dissolved in a solvent to form a solution. Examples thereof include a method of preparing and mixing both solutions, and then adding and mixing an alkali metal halide and / or an alkaline earth metal halide. The alkali metal halide and / or alkaline earth metal halide may be added in a dissolved state (for example, acetone, methyl ethyl ketone, etc.) in a solvent in which it is soluble, or You may add as it is, without dissolving in a solvent.

  The temperature at the time of reaction becomes like this. Preferably it is 30-100 degreeC, More preferably, it is 40-95 degreeC, More preferably, it is 60-90 degreeC. If the reaction temperature is too low, the substitution reaction may not proceed. On the other hand, if the reaction temperature is too high, the polyether rubber may be decomposed or the onium agent may be volatilized. Moreover, reaction time is not specifically limited, Usually, it is 0.5 to 10 hours, Preferably it is 2 to 8 hours. If the reaction time is too short, the substitution reaction may be incomplete. On the other hand, if the reaction time is too long, the polyether rubber may be decomposed.

（上記一般式（２）中、Ｒ’は炭素数１〜１０のアルキル基を示し、Ｘ’はハロゲン原子を表す。） In the production method of the present invention, a cyclic secondary amine such as pyrrole (in the present invention, a cyclic secondary amine is a nitrogen atom-containing aromatic heterocyclic compound). When one of the hydrogen atoms is bonded to the nitrogen atom in the ring, the same shall apply hereinafter), the “2” shown in the general formula (1) is used as necessary. The hydrogen atom bonded to the nitrogen atom in the ring bonded to the carbon atom in position can be substituted with a desired group. Specifically, after the reaction between the polyether rubber and the cyclic secondary amine, next, a base is mixed, a proton bonded to a nitrogen atom is eliminated, and further, for example, an alkyl halide is mixed. Then, a desired substituent can be introduced as shown in the following general formula (2).

(In the general formula (2), R ′ represents an alkyl group having 1 to 10 carbon atoms, and X ′ represents a halogen atom.)

  The method for recovering the cationized polyether rubber obtained by the above-mentioned onium reaction from the solvent is not particularly limited. For example, it is performed by appropriately combining coagulation, filtration and drying methods. These methods can be carried out in the same manner as in the case of the above-mentioned (non-cationized) polyether rubber.

  As described above, according to the present invention, a polyether rubber (cationized polyether rubber) containing 0.1 to 30 mol% of the unit represented by the general formula (1) is obtained. Can do. The polyether rubber obtained by the production method of the present invention contains the unit represented by the above general formula (1) in an amount of 0.1 mol% or more and less than 30 mol%, and therefore obtained by the production method of the present invention. The cross-linked rubber obtained from the polyether rubber has little variation in electric resistance value, low electric resistance value, and can suppress an increase in electric resistance value even when continuously used.

In the unit represented by the general formula (1), A ⁺ is a group containing a cationic nitrogen-containing aromatic heterocyclic ring. The group containing the cationic nitrogen-containing aromatic heterocyclic ring is located at the position “2” shown in the general formula (1) through one of the nitrogen atoms constituting the cationic nitrogen-containing aromatic heterocyclic ring. It is bonded to a carbon atom. The nitrogen-containing aromatic heterocyclic ring in the cationic nitrogen-containing aromatic heterocyclic ring in the group containing the cationic nitrogen-containing aromatic heterocyclic ring has a nitrogen atom in the ring and is particularly aromatic if it has aromaticity. It is not limited. For example, in the heterocyclic ring, in addition to the nitrogen atom bonded to the carbon atom at the position “2” shown in the general formula (1), it may have another nitrogen atom, an oxygen atom, a sulfur atom, etc. And may have a heteroatom other than a nitrogen atom, and a part of the atoms constituting the heterocyclic ring may be substituted with a substituent. Further, it may have a polycyclic structure in which two or more rings are condensed. Examples of the structure of such nitrogen-containing aromatic heterocycle include five-membered heterocycles such as imidazole ring, pyrrole ring, thiazole ring, oxazole ring, pyrazole ring, isoxazole ring; pyridine ring, pyrazine ring, pyrimidine ring, 6-membered heterocycles such as pyridazine ring and triazine ring; quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, cinnoline ring, purine ring, indole ring, isoindole ring, benzimidazole ring, benzoxazole ring, benzoisoxazole ring, etc. And the like. Among these, a 5-membered heterocyclic ring and a 6-membered heterocyclic ring are preferable, and an imidazole ring is more preferable. In the polyether rubber, A ⁺ in the unit represented by the general formula (1) is independent, and the polyether rubber contains two or more kinds of cationic nitrogen-containing aromatic heterocycles. Groups may be present.

  The substituent of the nitrogen-containing aromatic heterocycle is not particularly limited, and examples thereof include an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an arylalkyl group; an alkylaryl group; an alkoxyl group; Alkanol group; hydroxyl group; carbonyl group; alkoxycarbonyl group; amino group; imino group; nitrile group; alkylsilyl group; halogen atom;

（上記一般式（３）中に表されているＮ−は、上記一般式（１）において、上記一般式（１）に示す「２」の位置の炭素原子と結合している。また、上記一般式（３）中に表されているＲは、水素原子、または炭素数１〜２０の炭化水素基を表す。） In the present invention, the group containing a cationic nitrogen-containing aromatic heterocycle represented by A ⁺ in the general formula (1) is preferably a group represented by the following general formula (3).

(N— represented in the general formula (3) is bonded to the carbon atom at the position “2” shown in the general formula (1) in the general formula (1). R represented in the general formula (3) represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

  R represented in the general formula (3) is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group.

  In the polyether rubber obtained by the production method of the present invention, the content ratio of the unit represented by the general formula (1) is 0.1 mol% or more and less than 30 mol% in all monomer units, It is preferable that it is 0.5-25 mol%, and it is more preferable that it is 0.7-12 mol%. When the content ratio of the unit represented by the general formula (1) is within the above range, the rubber cross-linkage is low in compression set, low in electrical resistance, and capable of suppressing an increase in energization of the volume resistivity. A polyether rubber capable of providing a product is obtained. On the other hand, when the content ratio of the unit represented by the general formula (1) is too small, the volume specific resistance value of the obtained rubber cross-linked product is increased, and the electric resistance value is increased when voltage is continuously applied. There is a case. Moreover, when there is too much content rate of the unit represented by the said General formula (1), polyether rubber will become hard and the characteristic as a rubber elastic body may be lost.

The arbitrary counter anion represented by X ⁻ in the general formula (1) is a compound or atom having a negative charge bonded to A ^{+ through} an ionic bond, and other than having a negative charge Is not particularly limited. Since the counter anion is an ionizable ionic bond, at least a part of the counter anion can be exchanged for an arbitrary counter anion by a known ion exchange reaction. At the stage where the reaction is completed by mixing the oniumizing agent and polyether rubber containing an epihalohydrin monomer unit in a solution, X in the general formula (1) is a halogen atom. You may perform a well-known anion exchange reaction with respect to the halide ion which is ⁺ counter anion. The anion exchange reaction can be performed by mixing an ionic compound having ionization properties with a polyether rubber having an onium ion-containing group. The conditions for carrying out the anion exchange reaction are not particularly limited, but may be determined according to the structure of the ionic compound or polyether rubber used, the substitution rate of the target A ⁺ counter anion, and the like. The reaction may be carried out only with an ionic compound and a polyether rubber having an onium ion-containing group, or may contain other compounds such as an organic solvent. Although the usage-amount of an ionic compound is not specifically limited, 0.01-100 mol normally with respect to 1 mol of halogen atoms which comprise the epihalohydrin monomer unit to be used, Preferably it is 0.02-50 mol, More preferably It is the range of 0.03-10 mol. If the amount of the ionic compound is too small, the substitution reaction may be difficult to proceed. On the other hand, if the amount is too large, it may be difficult to remove the ionic compound.

  The pressure at the time of anion exchange reaction is usually 0.1 to 50 MPa, preferably 0.1 to 10 MPa, and more preferably 0.1 to 5 MPa. The temperature during the reaction is usually -30 to 200 ° C, preferably -15 to 180 ° C, more preferably 0 to 150 ° C. The reaction time is usually 1 minute to 1000 hours, preferably 3 minutes to 100 hours, more preferably 5 minutes to 10 hours, and even more preferably 5 minutes to 3 hours.

  The anion species of the counter anion is not particularly limited. For example, halide ions such as fluoride ion, chloride ion, bromide ion and iodide ion; sulfate ion; sulfite ion; hydroxide ion; carbonate ion; Ion; nitrate ion; acetate ion; perchlorate ion; phosphate ion; alkyloxy ion; trifluoromethanesulfonate ion; bistrifluoromethanesulfonimide ion; hexafluorophosphate ion; tetrafluoroborate ion; .

As a method for examining the content ratio of the unit represented by the general formula (1) in the polyether rubber obtained by the production method of the present invention (hereinafter also referred to as “onium ion unit content”), a known method is known. A method may be used. In order to obtain the onium ion unit content simply and quantitatively, the content of the onium ion-containing group may be quantified by performing ¹ H-NMR measurement on the polyether rubber obtained by the production method of the present invention. it can. Specifically, first, the number of moles B1 of all monomer units (including onium ion units) in the polymer is calculated from the integral value of protons derived from the polyether chain which is the main chain of the cationized polyether rubber. To do. Next, the number of moles B2 of the introduced onium ion unit (unit represented by the general formula (1)) is calculated from the integral value of protons derived from the onium ion-containing group. By dividing the number of moles B2 of the introduced onium ion unit (unit represented by the above general formula (1)) by the number of moles B1 of all monomer units (including the onium ion unit) in the polymer. The onium ion unit content can be calculated by the following formula.
Onium ion unit content (mol%) = 100 × B2 / B1

Further, when the onium agent used is not consumed in a reaction other than the substitution reaction of the onium ion-containing group under the reaction conditions described above, the molar amount of the onium agent consumed is the substitution mole of the halogen atom's onium ion-containing group. Equal to the amount. Therefore, the consumed molar amount of the onium agent is calculated by subtracting the residual molar amount A2 after the completion of the reaction from the added molar amount A1 before the start of the reaction, and the polyether rubber (hereinafter referred to as “reacted with the onium agent”) The onium ion unit content can also be calculated by the following formula by dividing by the molar amount P of all the monomer units of “base polyether rubber”.
Onium ion unit content (mol%) = 100 × (A1-A2) / P
For the measurement of the consumed molar amount, a known measurement method may be used. For example, the reaction rate is measured using a gas chromatography (GC) equipped with a capillary column and a flame ionization detector (FID). can do.

  Further, the polyether rubber obtained by the production method of the present invention essentially comprises the unit represented by the general formula (1), the unit represented by the general formula (1), [epihalohydrin monomer unit, and And / or a copolymer containing an unsaturated oxide monomer unit], a unit represented by the general formula (1), an ethylene oxide monomer unit, an [epihalohydrin monomer unit, and / or More preferably a copolymer containing an unsaturated oxide monomer unit], a unit represented by the above general formula (1), an ethylene oxide monomer unit, an epihalohydrin monomer unit, and an unsaturated oxide More preferably, it is a copolymer containing monomer units.

  The polyether rubber obtained by the production method of the present invention preferably contains a crosslinkable monomer unit. The crosslinkable monomer unit is preferably an epihalohydrin monomer unit and / or an unsaturated oxide monomer unit.

  As an epihalohydrin monomer, the epihalohydrin monomer which can be used for the polyether rubber containing 0.1 mol% or more of epihalohydrin monomer units mentioned above can be used. The content ratio of the epihalohydrin monomer unit in the polyether rubber obtained by the production method of the present invention is preferably 99.9 to 0 mol%, and 78.5 to 10 mol in all monomer units. % Is more preferable, and 57.3 to 15 mol% is particularly preferable. When the content ratio of the epihalohydrin monomer unit is within the above range, a polyether rubber capable of giving a rubber cross-linked product capable of suppressing an increase in current flow of the volume resistivity can be obtained. On the other hand, if the content ratio of the epihalohydrin monomer unit is too large, the volume specific resistance value of the resulting rubber cross-linked product may increase. If it is too low, the resulting cross-linked rubber cross-linked product is insufficiently cross-linked. It may be difficult to maintain the shape of the object.

  The unsaturated oxide monomer forming the unsaturated oxide monomer unit includes at least one carbon-carbon unsaturated bond (excluding the aromatic carbon-carbon unsaturated bond) and at least one epoxy in the molecule. And alkenyl glycidyl ethers such as allyl glycidyl ether and butenyl glycidyl ether; 3,4-epoxy-1-butene, 1,2-epoxy-5 Alkene epoxides such as hexene and 1,2-epoxy-9-decene; and the like. Among these, alkenyl glycidyl ethers are preferable, and allyl glycidyl ether is more preferable. An unsaturated oxide monomer may be used individually by 1 type, and may use 2 or more types together. The content ratio of the unsaturated oxide monomer unit in the polyether rubber obtained by the production method of the present invention is preferably 15 to 0 mol%, and 12 to 1 mol% in all monomer units. More preferably, it is 10 to 2 mol%. When the content ratio of the unsaturated oxide monomer unit in the polyether rubber is within the above range, a polyether rubber having excellent crosslinkability can be obtained. On the other hand, if the content ratio of the unsaturated oxide monomer unit is too small, the compression set of the resulting rubber cross-linked product may deteriorate. Further, if the content ratio of the unsaturated oxide monomer unit is too large, a gelling reaction (three-dimensional crosslinking reaction) or the like in the polymer molecule or between the polymer molecules is likely to occur during the polymerization reaction, and the molding processability is improved. May decrease.

  Further, when the polyether rubber obtained by the production method of the present invention is used as a material for a conductive member, particularly a conductive roll, the polyether rubber obtained by the production method of the present invention is made of ethylene from the viewpoint of low electrical resistance. It preferably contains an oxide monomer unit.

  The ethylene oxide monomer unit is a unit formed by an ethylene oxide monomer. The content ratio of the ethylene oxide monomer unit in the polyether rubber obtained by the production method of the present invention is preferably 90 to 0 mol%, and preferably 80 to 20 mol% in all monomer units. It is more preferable, and it is especially preferable that it is 75-40 mol%. When the content ratio of the ethylene oxide monomer unit in the polyether rubber is within the above range, a polyether rubber excellent in low electrical resistance can be obtained. On the other hand, when the content ratio of the ethylene oxide monomer unit is too small, it is difficult to obtain an effect of reducing the electric resistance value of the obtained rubber cross-linked product. Moreover, when there is too much content rate of an ethylene oxide monomer unit, there exists a possibility that manufacture of polyether rubber may become difficult.

  The polyether rubber obtained by the production method of the present invention is necessary in addition to the unit represented by the general formula (1), the epihalohydrin monomer unit, the unsaturated oxide monomer unit, and the ethylene oxide monomer unit. Depending on the above, it may be a copolymer containing the unit represented by the general formula (1) and another monomer unit copolymerizable with the monomer unit. Of the other monomer units, alkylene oxide monomer units excluding ethylene oxide are preferred. The alkylene oxide monomer that forms the alkylene oxide monomer unit excluding ethylene oxide is not particularly limited. For example, propylene oxide, 1,2-epoxybutane, 1,2-epoxy-4-chloropentane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxyisobutane, 2,3-epoxyisobutane, etc. A linear or branched alkylene oxide; cyclic alkylene oxides such as 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycyclododecane; butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2 -Methyloctylglycid Glycidyl ethers having alkyl linear or branched chain such as ether, neopentyl glycol diglycidyl ether, decyl glycidyl ether, stearyl glycidyl ether; oxyethylene side such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether Glycidyl ether having a chain; and the like. Among these, linear alkylene oxide is preferable, and propylene oxide is more preferable. These alkylene oxide monomers may be used individually by 1 type, and may use 2 or more types together. In the polyether rubber obtained by the production method of the present invention, the content of alkylene oxide monomer units excluding ethylene oxide is preferably 30 mol% or less, and 20 mol% in all monomer units. More preferably, it is more preferably 10 mol% or less. If the content ratio of the alkylene oxide monomer unit excluding ethylene oxide in the polyether rubber is too large, the volume specific resistance value of the resulting rubber cross-linked product may increase.

  The other copolymerizable monomers other than the alkylene oxide monomer are not particularly limited, and examples thereof include aryl epoxides such as styrene oxide and phenyl glycidyl ether. In the polyether rubber obtained by the production method of the present invention, the content ratio of other copolymerizable monomer units excluding the alkylene oxide monomer is preferably 20 mol% or less in all monomer units. 10 mol% or less is more preferable and 5 mol% or less is still more preferable.

  The weight average molecular weight of the polyether rubber obtained by the production method of the present invention is preferably 200,000 to 2,000,000, and more preferably 400,000 to 1,500,000. If the weight average molecular weight is too high, the Mooney viscosity becomes high and molding may be difficult. On the other hand, if the weight average molecular weight is too low, the compression set of the resulting rubber cross-linked product may be deteriorated.

The Mooney viscosity (polymer Mooney viscosity · ML _{1 + 4} , 100 ° C.) of the polyether rubber obtained by the production method of the present invention is preferably 10 to 120, and more preferably 20 to 90. If the Mooney viscosity is too high, the molding processability is inferior and it is difficult to form the conductive member. Furthermore, swell (the diameter of the extrudate becomes larger than the diameter of the die at the time of extrusion) may occur, and the dimensional stability may be reduced. On the other hand, if the Mooney viscosity is too low, the mechanical strength of the resulting rubber cross-linked product may be reduced.

<Crosslinkable rubber composition>
The crosslinkable rubber composition of the present invention is obtained by blending a polyether rubber obtained by the above-described production method of the present invention with a crosslinking agent.

  The cross-linking agent used in the present invention may be appropriately selected depending on the presence / absence of the cross-linkable monomer unit described above and the type thereof, as long as it can cross-link polyether rubber obtained by the production method of the present invention. There is no particular limitation. Examples of such cross-linking agents include sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur; sulfur monochloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, dibenzothiazyl disulfide, N , N′-dithio-bis (hexahydro-2H-azenopine-2), phosphorus-containing polysulfides, sulfur-containing compounds such as polymer polysulfides; organic peroxides such as dicumyl peroxide and ditertiarybutyl peroxide; p-quinone Quinone dioximes such as dioxime and p, p'-dibenzoylquinone dioxime; organic polyvalent amine compounds such as triethylenetetramine, hexamethylenediamine carbamate and 4,4'-methylenebis-o-chloroaniline; s-triazine -2,4,6-trithiol, etc. Triazine compounds; alkylphenol resins having a methylol group; and the like. Among these, sulfur, a sulfur-containing compound, and a triazine compound are preferable, and when an unsaturated oxide monomer is used as the crosslinkable monomer, sulfur and a sulfur-containing compound are more preferable. These crosslinking agents are used alone or in combination of two or more. The blending ratio of the crosslinking agent is 0.1 to 10 parts by weight, more preferably 0.2 to 7 parts by weight, and more preferably 0.3 to 5 parts by weight based on 100 parts by weight of the polyether rubber obtained by the production method of the present invention. Part by weight is more preferred. If the blending amount of the crosslinking agent is too small, the crosslinking speed becomes slow, and the productivity of the resulting rubber cross-linked product may decrease, or the abrasiveness may decrease when the rubber cross-linked product is used after being polished. . On the other hand, when there are too many compounding quantities of a crosslinking agent, there exists a possibility that the hardness of the rubber crosslinked material obtained may become high, or a crosslinking agent may bloom.

  When sulfur or a sulfur-containing compound is used as the crosslinking agent, it is preferable to use a crosslinking accelerator and a crosslinking accelerator in combination. The crosslinking acceleration aid is not particularly limited, and examples thereof include zinc white and stearic acid. Although it does not specifically limit as a crosslinking accelerator, For example, guanidine type | system | group; Aldehyde type | system | group; Aldehyde type | system | group ammonia type | system | group; Thiazole type | system | group; Sulfenamide type | system | group; Accelerators can be used. One crosslinking accelerator and one crosslinking accelerator may be used alone, or two or more thereof may be used in combination.

  Each amount of the crosslinking accelerator and the crosslinking accelerator is not particularly limited, but is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the polyether rubber obtained by the production method of the present invention. 1-10 weight part is more preferable. If the amount of the crosslinking accelerator and the crosslinking accelerator used is too large, the crosslinking rate may become too fast or the surface of the resulting rubber crosslinked product may bloom. On the other hand, when the amount is too small, the crosslinking rate is slow and the productivity is inferior, or the crosslinking does not proceed sufficiently, and the resulting rubber cross-linked product may be inferior in mechanical properties.

  The crosslinkable rubber composition of the present invention includes butadiene rubber, styrene butadiene rubber, chloroprene rubber, isoprene rubber, natural rubber, acrylonitrile butadiene rubber, butyl rubber, and partially hydrogenated products of these rubbers within a range not impairing the effects of the present invention. Diene rubbers such as (for example, hydrogenated nitrile rubber); rubbers other than diene rubbers such as ethylene propylene rubber, acrylic rubber, polyether rubber (excluding the polyether rubber of the present invention), fluorine rubber, and silicone rubber; Thermoplastic elastomers such as olefin-based thermoplastic elastomers, styrene-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers; polyvinyl chloride May contain; coumarone resin, resins such as phenol resin. These rubbers, thermoplastic elastomers, and resins can be used alone or in combination of two or more, and the total content thereof is based on 100 parts by weight of the polyether rubber obtained by the production method of the present invention. 100 parts by weight or less, more preferably 50 parts by weight or less, and particularly preferably 20 parts by weight or less.

  Furthermore, the crosslinkable rubber composition of the present invention may contain other additives usually blended with known rubbers in addition to the additives described above. Examples of such additives include, but are not limited to, fillers; acid acceptors; reinforcing agents; anti-aging agents; ultraviolet absorbers; light stabilizers; tackifiers; surfactants; Examples include electrolyte substances; colorants (dyes and pigments); flame retardants; antistatic agents;

  The crosslinkable rubber composition of the present invention is prepared by blending and kneading a crosslinker and each additive used as necessary to the polyether rubber obtained by the production method of the present invention by a desired method. be able to. For example, a crosslinkable rubber composition can be obtained by kneading an additive excluding a crosslinking agent and a crosslinking accelerator and a polyether rubber and then mixing the mixture with the crosslinking agent and the crosslinking accelerator. In blending and kneading, for example, one or a combination of any kneading and molding machines such as a kneader, a banbury, an open roll, a calender roll, and an extruder may be used for kneading and molding. The kneading temperature of the additive excluding the crosslinking agent and crosslinking accelerator and the polyether rubber is preferably 20 to 200 ° C, more preferably 20 to 150 ° C, and the kneading time is preferably 30 seconds to 30 minutes. The mixing temperature of the product, the crosslinking agent and the crosslinking accelerator is preferably 100 ° C. or less, more preferably 0 to 80 ° C.

<Rubber cross-linked product>
The rubber cross-linked product of the present invention is obtained by cross-linking the cross-linkable rubber composition of the present invention described above.

  The method for cross-linking the cross-linkable rubber composition of the present invention is not particularly limited, and the forming and cross-linking may be performed simultaneously or after forming. 20-200 degreeC is preferable and the temperature at the time of shaping | molding has more preferable 40-180 degreeC. 130-200 degreeC is preferable and the heating temperature at the time of bridge | crosslinking has more preferable 140-200 degreeC. If the temperature at the time of crosslinking is too low, the crosslinking time may be required for a long time, or the crosslinking density of the resulting rubber crosslinked product may be lowered. On the other hand, if the temperature at the time of crosslinking is too high, there is a risk of forming defects. The crosslinking time varies depending on the crosslinking method, crosslinking temperature, shape, etc., but a range of 1 minute or more and 5 hours or less is preferable from the viewpoint of crosslinking density and production efficiency. As a heating method, a method such as press heating, oven heating, steam heating, hot air heating, and microwave heating may be appropriately selected.

  Further, depending on the shape and size of the rubber cross-linked product, even if the surface is cross-linked, it may not be sufficiently cross-linked to the inside. Therefore, secondary cross-linking may be performed by heating. 100-220 degreeC is preferable and the heating temperature in performing a secondary bridge | crosslinking has more preferable 130-210 degreeC. The heating time is preferably 30 minutes to 5 hours.

The volume specific resistance value of the rubber cross-linked product of the present invention is usually 1 × 10 ^{4 at} a value of 30 V from the start of voltage application in a measurement environment where the temperature is 23 ° C. and the humidity is 50%. ^1.0 to 1 × 10 ^9.5 Ω · cm, preferably 1 × 10 ^4.5 to 1 × 10 ^8.0 Ω · cm, and more preferably 1 × 10 ^5.0 to 1 × 10 ^{7. .2} Ω · cm. When the volume specific resistance value of the rubber cross-linked product is within the above range, a conductive member excellent in low electrical resistance can be obtained. On the other hand, if the volume specific resistance value of the rubber cross-linked product is too high, a higher voltage must be applied in order to pass the same current, and the amount of power consumption increases, which is not suitable for a conductive member. Moreover, when the volume specific resistance value of the rubber cross-linked product is too low, a current flows in an unintended direction other than the voltage application direction, which may impair the function as a conductive member.

The increase in energization of the volume specific resistance value of the rubber cross-linked product of the present invention is 30 from the start of voltage application from log ₁₀ (volume specific resistance value) 10 minutes after the start of voltage application under the measurement conditions of the volume specific resistance value. In a case where log ₁₀ (volume specific resistance value) after 2 seconds is reduced, it is preferably in the range of 0 to 0.5.

  The rubber cross-linked product of the present invention thus obtained has little variation in electric resistance value, low electric resistance value, and suppresses an increase in electric resistance value even when continuously used. It can be suitably used for a conductive member used in a printing machine or the like, particularly a conductive roll.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The “parts” in each example are based on weight unless otherwise specified.
Various physical properties were evaluated according to the following methods.

[Onium ion unit content]
The onium ion unit content was measured as follows using a nuclear magnetic resonance apparatus ( ¹ H-NMR). After the onium reaction, 30 mg of a polyether rubber obtained by coagulation and drying was added to 1.0 ml of dimethyl sulfoxide, and the mixture was uniformly dissolved by shaking for 1 hour. The onium ion unit content rate was computed by measuring this solution by < ¹ > H-NMR. First, the number of moles B1 of all monomer units (including onium ion units) in the polymer was calculated from the integral value of protons derived from the polyether chain which is the main chain of the polyether rubber. Next, the number of moles B2 of the introduced onium ion unit (unit represented by the general formula (1)) was calculated from the integral value of protons derived from the onium ion-containing group. The mole number B2 of the introduced onium ion unit (unit represented by the general formula (1)) is divided by the mole number B1 of all monomer units (including the onium ion unit) in the polymer. Thus, the onium ion unit content was calculated by the following formula.
Onium ion unit content (mol%) = 100 × B2 / B1

[Mooney viscosity]
Mooney viscosity (ML _{1 + 4} , 100 ° C.) was measured at 100 ° C. according to JIS K6300.

(Production Example 1, production of polymerization catalyst)
The sealed pressure-resistant glass container was replaced with nitrogen, and 200 parts of toluene and 60 parts of triisobutylaluminum were supplied. The glass container was immersed in ice water and cooled, and then 230 parts of diethyl ether was added and stirred. Next, while cooling with ice water, 13.6 parts of phosphoric acid was added and further stirred. At this time, due to the reaction between triisobutylaluminum and phosphoric acid, the internal pressure of the container increased, and therefore depressurization was carried out in a timely manner. Next, the obtained reaction mixture was aged in a 60 ° C. warm water bath for 1 hour to obtain a catalyst solution.

(Production Example 2, Production of Polyether Rubber A)
Into an autoclave, 223.5 parts of epichlorohydrin, 27.5 parts of allyl glycidyl ether, 19.7 parts of ethylene oxide and 2585 parts of toluene were added, and the temperature of the inner solution was raised to 50 ° C. while stirring in a nitrogen atmosphere. 11.6 parts of the catalyst solution obtained in 1 above was added to start the reaction. Next, a solution prepared by dissolving 129.3 parts of ethylene oxide in 302 parts of toluene was continuously added at a constant rate over 5 hours from the start of the reaction. Further, every 30 minutes after the start of the reaction, 6.2 parts of the catalyst solution was added over 5 hours. Next, 15 parts of water was added and stirred to terminate the reaction. Furthermore, 45 parts of a 5% toluene solution of 4,4′-thiobis- (6-tert-butyl-3-methylphenol) was added as an antioxidant and stirred. Steam stripping was performed to remove toluene, and supernatant water was removed, followed by vacuum drying at 60 ° C. to obtain 400 parts of polyether rubber A. As a result of measurement by ¹ H-NMR, the monomer composition ratio of the obtained polyether rubber A was as follows: epichlorohydrin monomer unit 40 mol%, ethylene oxide monomer unit 56 mol%, allyl glycidyl ether unit The monomer unit was 4 mol%. The resulting polyether rubber A had a Mooney viscosity of 60.

[Example 1]
In 900 parts of toluene, 100 parts of the polyether rubber A obtained in Production Example 1 was added and dissolved by stirring. Next, 11.13 parts of an acetone solution of sodium iodide (prepared by dissolving 1.13 parts of sodium iodide in 10 parts of acetone) and 1.24 parts of 1-methylimidazole are added to the obtained solution. Then, the mixture was stirred for 2 minutes at 10,000 rpm using a stirrer to obtain a polyether rubber A cement. Then, the obtained polyether rubber A cement was shaken in a water bath at 75 ° C. for 6 hours using a shaker, so that polyether rubber A and 1 were added in the presence of sodium iodide. -Methylimidazole was reacted (onium reaction) to synthesize cationized polyether rubber 1. Then, by dropping the cement after the reaction into isooctane, the cationized polyether rubber 1 contained in the cement is coagulated, and the solvent is removed by vacuum drying the cationized polyether. Rubber 1 was recovered with a yield of 98 parts.

And about the obtained cationized polyether rubber 1, the onium ion unit content rate was computed by measuring < ¹ > H-NMR according to the method mentioned above. The cationized polyether rubber 1 thus obtained had an onium ion unit content of 1.9 mol%. That is, the monomer composition ratio of the obtained cationized polyether rubber 1 is as follows: epichlorohydrin monomer unit 38.1 mol%, ethylene oxide monomer unit 56 mol%, onium ion unit (general formula ( The unit represented by 1) was 1.9 mol%, and the allyl glycidyl ether monomer unit was 4 mol%. Further, the Mooney viscosity of the obtained cationized polyether rubber 1 was 50.

[Example 2]
In Example 1, the onium reaction was carried out using a shaker in a 75 ° C. water bath under conditions of shaking for 6 hours, but instead, using a stirrer, an 80 ° C. A cationized polyether rubber 2 was obtained in the same manner as in Example 1 except that the onium reaction was carried out by stirring for 7 hours at 400 rpm in a water bath.

And about the obtained cationized polyether rubber | gum 2, according to the method mentioned above, the onium ion unit content rate was computed by measuring < ¹ > H-NMR. The obtained cationized polyether rubber 2 had an onium ion unit content of 1.8 mol%. That is, the monomer composition ratio of the obtained cationized polyether rubber 1 was as follows: epichlorohydrin monomer unit 38.2 mol%, ethylene oxide monomer unit 56 mol%, onium ion unit (general formula ( The unit represented by 1) was 1.8 mol%, and the allyl glycidyl ether monomer unit was 4 mol%. The resulting cationized polyether rubber 1 had a Mooney viscosity of 48.

[Comparative Example 1]
Onionization was performed in the same manner as in Example 1, except that sodium iodide was not used (that is, only 10 parts of acetone was added instead of the acetone solution of sodium iodide). Reaction was performed. Then, the polyether rubber obtained after onium reaction, according to the method described above, by measuring ^{1 H-NMR,} was calculated onium ion unit content, the onium ion unit content was 0%, It was confirmed that the onium reaction did not proceed substantially.

[Comparative Example 2]
In carrying out the onium reaction, the onium reaction was carried out in the same manner as in Example 2 except that 5 parts of water was added instead of 11.13 parts of the acetone solution of sodium iodide. Then, the polyether rubber obtained after onium reaction, according to the method described above, by measuring ^{1 H-NMR,} was calculated onium ion unit content, the onium ion unit content was 0%, It was confirmed that the onium reaction did not proceed substantially.

As shown in Table 1, when a polyether rubber containing an epihalohydrin monomer unit and a nitrogen atom-containing aromatic heterocyclic compound are reacted in a solution, an alkali metal halide and / or an alkaline earth is reacted. When using a halide of a similar metal, it was possible to favorably proceed the oniumation reaction even in a solution (Examples 1 and 2).
On the other hand, when no alkali metal halide and / or alkaline earth metal halide was used, the oniumation reaction did not proceed (Comparative Examples 1 and 2).

Claims (5)

A method for producing a polyether rubber containing a unit represented by the following general formula (1) in an amount of 0.1 mol% or more and less than 30 mol%,
A polyether rubber containing 0.1 mol% or more of epihalohydrin monomer unit and a nitrogen atom-containing aromatic heterocyclic compound in the presence of an alkali metal halide and / or an alkaline earth metal halide. A polyether rubber characterized by replacing at least part of the halogen atoms constituting the epihalohydrin monomer unit with a group containing a cationic nitrogen-containing aromatic heterocycle by reacting in a solution. Manufacturing method.

(In the above general formula (1), A ⁺ is a group containing a cationic nitrogen-containing aromatic heterocycle. The group containing the cationic nitrogen-containing aromatic heterocycle is the cationic nitrogen-containing aromatic heterocycle. It is bonded to the carbon atom at the position “2” shown in the general formula (1) through one of the nitrogen atoms constituting the heterocyclic ring. X ⁻ is an arbitrary counter anion.)   2. The method for producing a polyether rubber according to claim 1, wherein the alkali metal halide and / or the alkaline earth metal halide is an alkali metal iodide.   A polyether rubber obtained by the production method according to claim 1.   A crosslinkable rubber composition comprising the polyether rubber according to claim 3 and a crosslinking agent.   A rubber cross-linked product obtained by cross-linking the cross-linkable rubber composition according to claim 4.