TW201615618A - Bis-alkylidene diamino guanidine and salt thereof, modified rubber, rubber composition, and tire - Google Patents

Abstract

The present invention provides a compound represented by formula (1) or formula (2). In the formula, X represents an acid that forms a salt with the guanidine site, and each of R1 and R2 independently represents at least one moiety selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, alkyl aryl groups and alkenyl groups having a carbon number of 1 to 18 (wherein each of these groups include those groups that have one or more substituents containing a sulfur atom, nitrogen atom or oxygen atom), and a hydrogen atom. In the formula, each of R1 and R2 each independently represents at least one moiety selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, alkyl aryl groups and alkenyl groups having a carbon number of 1 to 18 (wherein each of these groups include those groups that have one or more substituents containing a sulfur atom, nitrogen atom or oxygen atom), and a hydrogen atom.

Description

Bisalkylenediamine oxime and its salts, modified rubber, rubber composition, and tire

The present invention relates to novel bisalkylene diamine hydrazines and salts thereof, modified rubbers, rubber compositions, and tires.

A synthetic raw material such as an amine-based oxime-based medicine, a dye, a photographic drug, or a gunpowder is widely known in the medical field, and its anti-glycation action is known (see Non-Patent Document 1). The anti-glycation action of the aminoguanidine has been confirmed to inhibit the formation of AGEs in the in vitro test, inhibit the cross-linking of proteins, the formation of a polymerization, prevent kidney disease, retinopathy, neuropathy in diabetic animals, and prevent the progression of diabetic complications. Effect (refer to Non-Patent Document 2).

In recent years, in addition to the above-mentioned uses, the amine-based oxime has also been found to be an absorbent for an odor component of an aldehyde, that is, an aldehyde collector (Catcher) (see Patent Document 1), and a rubber additive (refer to the patent document). 2). The physical properties required for such applications are increasingly diversified and it is required to provide compounds for replacing the conventional amine-based oxime.

On the other hand, the filler used for rubber is a blending agent used for the purpose of reinforcing or increasing the rubber or imparting a special function to the rubber. Carbon black, which is a representative filler, contributes not only to the mechanical properties (reinforcing effect) such as the elastic modulus and breaking strength of the rubber, but also to impart conductivity and the like.

As a method of obtaining a rubber reinforcing effect similarly to carbon black, a method of obtaining a rubber composition having low heat generation, that is, a low loss property can be obtained. Conventionally, a method of using an inorganic filler such as cerium oxide has been known, and it is applied to environmental considerations. Low fuel cost, tire-oriented rubber composition, and the like.

a rubber composition in which an inorganic filler is blended, and when the inorganic filler is blended, the inorganic filler, particularly the hydrophilic cerium oxide having a sterol group on the surface, has a low affinity with the hydrophobic rubber, and Since it is agglomerated in the rubber composition, it is necessary to improve the affinity between the cerium oxide and the rubber in order to improve the reinforcing property by using cerium oxide and to obtain a low heat generating effect. The method is known in which a synthetic rubber which is improved in affinity with an inorganic filler by terminal modification by a polar group (see Patent Document 3) or a copolymer with a monomer having a polar group is used. A synthetic rubber having an improved affinity between inorganic fillers (see Patent Document 4). As a method of introducing a polar group by modifying a natural rubber, a method of modifying a natural rubber by a ruthenium compound having a polar group (refer to Patent Document 5) and coupling a decane is known. The agent is added to a rubber composition containing a modified natural rubber and a cerium oxide to which a polar group has been introduced to further improve the dispersibility of cerium oxide (see Patent Document 6). [Prior technical literature] [Non-patent literature]

[Non-Patent Document 1] "Salt Salt", Fine Chemicals, CMC Publishing, June, 2008, Vol. 37, No. 6, p. 72-75 [Non-Patent Document 2] Naito Yuko and one other person, "Function and Development of Anti-Glycation Targeting Materials in the Body" Exquisite Chemicals, CMC Publishing, June 24, 2005, Vol. 41, No. 6, p. 21-26 [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. 2010-248334 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-209253 (Patent Document 4) Japanese Patent Laid-Open No. 2011-38009 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2009-108204 (Patent Document 6)

[The subject to be solved by the invention]

However, it is expected that the world's interest in environmental problems such as carbon dioxide concentration and air pollution in the atmosphere will increase in the future, and it is necessary to provide a modified rubber that contains a reduction in the rotational resistance of the tire and is associated with a low fuel cost of the automobile. A rubber composition excellent in low loss of the inorganic filler such as the modified rubber and cerium oxide, and a tire technology.

The present invention has been made in view of the above problems in the prior art, and it is an object of the invention to provide a novel novel bisalkylenediamine fluorene and a salt thereof which are useful as a rubber additive. [Means for solving the problem]

The inventors of the present invention have diligently studied, and as a result, the novel bisalkylenediamine fluorene and its salt have been successfully produced, and the present invention has been completed.

That is, the present invention is as follows.

[1] a compound represented by formula (1) or formula (2); In the formula, X is an acid which forms a salt with a hydrazine moiety, and R ¹ and R ² are each independently selected from an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, and an alkenyl group ( Each of the groups includes at least one selected from the group consisting of one or more substituents containing a sulfur atom, a nitrogen atom or an oxygen atom, and a hydrogen atom; In the formula, R ¹ and R ² are each independently selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, and an alkenyl group (all of which include one or more). At least one of the group consisting of a sulfur atom, a nitrogen atom, or a substituent of an oxygen atom, and a hydrogen atom. [2] The compound of [1] obtained by reacting a compound represented by the formula (3) with a compound represented by the formula (4); Wherein the X-form and the hydrazine moiety of the formula (3) form a salt acid; In the formula, R ¹ and R ² are each independently selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, and an alkenyl group (all of which include one or more At least one of the group consisting of a sulfur atom, a nitrogen atom, or a substituent of an oxygen atom, and a hydrogen atom. [3] The compound of [1] or [2], wherein R ¹ and R ^{2 of the} formula (1) or the formula (2) are each independently selected from an alkyl group having 1 to 8 carbon atoms and an aryl group. At least one of the group consisting of an alkenyl group and a hydrogen atom. [4] The compound according to any one of [1] to [3], which has a melting point of 50 to 300 °C. [5] The compound according to any one of [1] to [4], which is represented by any one of the formulae (5) to (10), and (12) to (14); 【化6】 【化7】 【化8】 【化9】 【化10】 【化11】 【化12】 【化13】 [6] A modified rubber (A), which is obtained by a compound according to any one of [1] to [5], which is selected from the group consisting of natural rubber and synthetic rubber. Obtained by modification. [7] The modified rubber (A) according to [6], wherein the at least one rubber selected from the group consisting of natural rubber and synthetic rubber is represented by the formula (1) or (2) The compound is obtained by mixing and modifying at a temperature of 20 to 180 °C. [8] The modified rubber (A) according to [6] or [7], wherein the compound represented by the formula (1) or the formula (2) is used in an amount of 0.01% relative to the total amount of the natural rubber and the synthetic rubber. 10% by mass. [9] A rubber composition comprising the modified rubber (A) according to any one of [6] to [8], a filler containing the inorganic filler (B), and a decane coupling agent (C). [10] The rubber composition according to [9], wherein the inorganic filler (B) is cerium oxide. [11] The rubber composition of [9] or [10], wherein the filler material comprises carbon black. [12] A rubber composition comprising the modified rubber (A) according to any one of [9] to [11], which is a compound represented by the formula (1) or (2), which is selected from the group consisting of At least one rubber of the group consisting of natural rubber and synthetic rubber, the filler containing the inorganic filler (B), and the decane coupling agent (C) are mixed. [13] The rubber composition of [12], wherein the temperature at the time of mixing is in the range of 20 to 180 °C. [14] The rubber composition of [12] or [13], wherein the compound represented by the formula (1) or the formula (2) is used in an amount of 0.01 to 10 relative to the total amount of the natural rubber and the synthetic rubber. quality%. [15] A tire which is a rubber composition according to any one of [9] to [14], which is applied to a tread of a tire member. [Effects of the Invention]

The bisalkylenediamine fluorene of the present invention and salts thereof are useful as rubber additives and the like.

Hereinafter, the form for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described in detail. The following examples are intended to illustrate the invention and are not intended to limit the invention to the following. The present invention can be carried out with appropriate changes within the scope of the gist of the invention.

<Bis-alkylenediamine oxime and its salt> The compound of the present embodiment is a compound represented by the formula (1) or the formula (2) (hereinafter also referred to as "bis-alkylenediamine oxime", "double-Asia" An alkyldiamine sulfonium salt, or a "bisalkylenediamine hydrazine or a salt thereof"). 【化14】 In the formula, X is an acid which forms a salt with a hydrazine moiety, and R ¹ and R ² are each independently selected from an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, and an alkenyl group ( Each of the groups includes at least one selected from the group consisting of one or more substituents containing a sulfur atom, a nitrogen atom or an oxygen atom, and a hydrogen atom; In the formula, R ¹ and R ² are each independently selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, and an alkenyl group (all of which include one or more). At least one of the group consisting of a sulfur atom, a nitrogen atom, or a substituent of an oxygen atom, and a hydrogen atom.

The X of the formula (1) is not particularly limited, and examples thereof include organic acids and inorganic acids, and more specifically, hydrochloric acid, sulfuric acid, carbonic acid, nitric acid, acetic acid, oxalic acid, phosphoric acid, p-toluenesulfonic acid, hydrobromic acid, and hydrogen iodine. Acid, amine sulfonic acid, perchloric acid, citric acid, boric acid, phenylphosphinic acid, and the like. Among these, hydrochloric acid, sulfuric acid, carbonic acid, and nitric acid which are commercially easy to obtain the onium salt of the raw material compound are preferable, and the ease of purification at the time of production is considered, and hydrochloric acid and carbonic acid are more preferable.

In the compound of the present embodiment, in the formula (1) or (2), R ¹ and R ² are each independently selected from an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group or an alkylaryl group. And at least one selected from the group consisting of alkenyl groups (each of which includes one or more substituents containing a sulfur atom, a nitrogen atom, or an oxygen atom) and a hydrogen atom, and is preferably selected from the group consisting of At least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkenyl group, and a hydrogen atom is preferred.

Specific examples of such a substituent are not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, a pentyl group, and a 1-methyl group. Butyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 2-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropane Base, 2,2-dimethylpropyl, vinyl, 1-methylvinyl, 2-methylvinyl, 1-ethylvinyl, 2-ethylvinyl, 1,2-dimethyl Vinyl, 1-propylvinyl, 1-isopropylvinyl, 1-ethyl-2-methylvinyl, 2-ethyl-1-methylvinyl, 1-butylvinyl, 1 - a second butyl vinyl group, a 1-tert-butyl vinyl group, a 1-isobutyl vinyl group, a 2-butyl vinyl group, a 2-second butyl vinyl group, a 2-tert-butyl vinyl group, 2-isobutylvinyl, 2-methyl-1-propylvinyl, 2-methyl-1-isopropylvinyl, 1,2-diethylvinyl, 1-methyl-2- Propylvinyl, 1-methyl-2-isopropylvinyl, 2-phenylvinyl, etc., preferably methyl, ethyl, isopropyl, butyl, pentyl, vinyl, 1-methyl Vinyl, 2-methylvinyl, 2- Vinyl preferred.

Specific examples of the compound represented by the formula (1) or the formula (2) of the present embodiment are not particularly limited, and examples thereof include bisethylenediamine sulfonium (salt) and bispropylenediamine sulfonium (salt). , dibutylene diamino sulfonium (salt), bis(2-methylpropylene)diamine sulfonium (salt) represented by formula (11), bis-pentylenediamine sulfonium (salt), double ( 2-methylbutylene)diamine sulfonium (salt), bis(3-methylbutylidene)diamine sulfonium (salt), bis(2,2-dimethylpropylene)diamine hydrazine ( Salt), bis-hexamethylenediamine sulfonium (salt), bis(2-methylpentylene)diamine sulfonium (salt), bis(3-methylpentylene)diamine sulfonium (salt), Bis(4-methylpentylene)diamine sulfonium (salt), bis(2,3-dimethylbutylidene)diamine sulfonium (salt), bis(2,2-dimethylbutylene) Diamino sulfonium (salt), bis(3,3-dimethylbutylidene)diamine sulfonium (salt), bis(1-methylethylidene)diamine sulfonium (salt), formula (14) Bis(1-methylpropylene)diamine sulfonium (salt), bis(1,2-dimethylpropylene)diamine sulfonium (salt) represented by formula (5), double (1) -Methylbutylene)diamine sulfonium (salt), bis(1,2-dimethylbutylidene)diamine sulfonium (salt), bis(1,3-dimethylbutylene)diamine Hydrazine (salt), bis(1-methylpentylene)diamine sulfonium (salt) represented by formula (6), bis(1-methylhexylene)diamine hydrazine represented by formula (7) ), bis(1-ethylpropylene)diamine sulfonium (salt), bis(1-isopropyl-2-methylpropylene)diamine sulfonium (salt), represented by formula (12) Diamethylenediamine sulfonium (salt), bis(1-methylallyl)diamine sulfonium (salt), bis(1-ethylallyl)diamine sulfonium (salt) , bis(1-propylallyl)diamine sulfonium (salt), bis(2-methylallyl)diamine sulfonium (salt) represented by formula (8), bis(1,2) - dimethylallyl)diamine sulfonium (salt), bis(2-ethylallyl)diamine sulfonium (salt), bis(2-propylalenyl)diamine Bismuth (salt), bis(2-isopropylallyl)diamine sulfonium (salt), bis(2-butylallyl)diamine sulfonium (salt), bis(2-isobutyl) Allyl)diamine sulfonium (salt), bis(2-second butylallyl)diamine sulfonium (salt), bis(2-t-butylallyl)diamine Base (salt), bis(2-(1-methylbutyl)allyl)diamine sulfonium (salt), bis(2-(2-methylbutyl)alenylene)diamine Base (salt), bis(2-(3-methylbutyl)alenylene) Amine sulfonium (salt), bis(2-(1-ethylpropyl)allyl)diamine sulfonium (salt), bis(2-(2-ethylpropyl)allyl) Amine bismuth (salt), bis(2-(1,1-dimethylpropyl)allyl)diamine sulfonium (salt), bis(2-(2,2-dimethylpropyl) Allyl)diamine sulfonium (salt), bis(3-methylallyl)diamine sulfonium (salt) represented by formula (9), bis(3-ethylallyl) Amine sulfonium (salt), bis(3-propylallyl)diamine sulfonium (salt), bis(3-isopropylallyl)diamine sulfonium (salt), bis (3- Butylallyl)diamine sulfonium (salt), bis(3-isobutylallyl)diamine sulfonium (salt), bis(3-butylbutylallyl)diamine Base (salt), bis(3-t-butylallyl)diamine sulfonium (salt), bis(3-(1-methylbutyl)allyl)diamine sulfonate , bis(3-(2-methylbutyl)allyl)diamine sulfonium (salt), bis(3-(3-methylbutyl)allyl)diamine sulfonium (salt) , bis(3-(1,1-dimethylpropyl)allyl)diamine sulfonium (salt), bis(3-(2-ethylpropyl)allyl)diamine Bismuth (salt), bis(3-(1,2-dimethylpropyl)allyl)diamine sulfonium (salt), bis(3-(2,2-dimethyl) Propyl)allyl)diamine sulfonium (salt), bis(3-phenylallyl)diamine sulfonium (salt), formula (10) and formula (13) Methyl-3-phenylallyl)diamine sulfonium (salt) and the like.

Among the compounds represented by the above formula (1) or (2), a compound other than the compound represented by the following formula (11) is preferred.

【化16】

Further, among the compounds represented by the above formula (1) or formula (2), preferred compounds are compounds represented by the following formulas. 【化17】

【化18】

【化19】

【化20】

【化21】

【化22】

【化23】

【化24】

【化25】

The compound represented by the formula (1) or the formula (2) of the present embodiment can be obtained by a known method, and for example, a compound represented by the formula (3) ("1,3-diamine sulfonium salt", also referred to as "salt salt" can be obtained. ") is obtained by reacting with a compound represented by the formula (4) (also referred to as "carbonyl compound"). Such a manufacturing method is preferable from the viewpoint of manufacturing cost. More specifically, the compound represented by the formula (1) or the formula (2) can be obtained by reacting the compound represented by the formula (3) with the acetone represented by the formula (4) to form an alkylene skeleton, and the methyl ethyl ketone is equivalent to an alcohol such as water or methanol. In the solvent, an acid is added as needed to cause it to be obtained. 【化26】 Wherein the X-form and the hydrazine moiety of the formula (3) form a salt acid; In the formula, R ¹ and R ² are each independently selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, and an alkenyl group (all of which include one or more At least one of the group consisting of a sulfur atom, a nitrogen atom, or a substituent of an oxygen atom, and a hydrogen atom.

The compound represented by the formula (1) or the formula (2) is usually a salt represented by the formula (1), but a compound which is not a salt represented by the formula (2) is also obtained. When a salt is formed, an acid represented by the formula (1) can be appropriately selected to form a salt acid in accordance with, for example, the compound represented by the formula (3) and the type of the acid to be added.

The compound represented by the formula (1) or the formula (2) is usually a salt represented by the formula (1), but the kind and production conditions of the compound represented by the formula (4) may be relative to the formula (1) or the formula (1). 2) The compound 1 is an acid used in a molar amount of 1 mol or less, and does not form a salt with an acid.

The compound represented by the formula (3) is strongly alkaline due to the positive charge resonance of the conjugate acid in the majority of the nitrogen atoms present in the molecule, and is usually present in the form of a complex (salt) with an acid. The compound represented by the formula (3) is not particularly limited, and specific examples thereof include 1,3-diaminophosphonium carbonate, 1,3-diaminophosphonium hydrochloride, and 1,3-diaminophosphonium hydroxide. Acid salt, 1,3-diamino sulfonium sulfate, 1,3-diamine hydrazine nitrate, 1,3-diamino oxalate, 1,3-diaminophosphonium phosphate, 1, 3-diaminopurine acetate, 1,3-diamine decyl sulfonate, 1,3-diamine hydrazine perchlorate, 1,3-diaminohydrazine hydrobromide, 1, 3-diamine decanoate, 1,3-diaminophosphonium borate, 1,3-diaminophosphonium phenylphosphonate, and the like. Among these, 1,3-diamino guanidine hydrochloride is commercially easily obtain the 1,3-diamino guanidine sulfate, 1,3-diamino guanidine carbonate, 1,3-diamine The nitroxide is preferred, and the ease of refining at the time of manufacture is considered, and 1,3-diaminophosphonium carbonate and 1,3-diaminophosphonium hydrochloride are preferred.

The compound represented by the formula (4) is not particularly limited, and R ¹ and R ² are selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, and an alkenyl group (all of which include At least one selected from the group consisting of one or more substituents containing a sulfur atom, a nitrogen atom, or an oxygen atom, and a hydrogen atom selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an aryl group, and It is preferred that at least one of the group consisting of an alkenyl group and a hydrogen atom is economically easy to obtain or can be used in an aqueous solvent.

Specific examples of the compound represented by the formula (4) are not particularly limited, and examples thereof include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, methyl-third butanone, and 2-pentanone. -Hexanone, 2-heptanone, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, 2-methylbutanal, trimethylacetaldehyde, acrolein, methacryl Aldehyde, crotonaldehyde, 2-pentenal, 2-hexenal, 2-heptanal, 2-octanal, benzalacetone, etc., in which the consideration of commercial easiness is considered, acetone, methyl ethyl ketone, diethyl ketone, Methyl isopropanone, methyl isobutyl ketone, 2-pentanone, 2-hexanone, 2-heptanone, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, acrolein, methacrolein, croton Aldehyde and benzylideneacetone are preferred.

These carbonyl compounds are all known compounds and can be obtained in the form of a commercial product. Further, some compounds may have an isomer of a trans form and a cis form like crotonaldehyde, and such a mixture of a trans form and a cis form, and only a trans form compound may be used.

The reaction conditions of the compound represented by the formula (3) and the compound represented by the formula (4) will be described in detail. The reaction is, for example, relative to the compound 1 mol represented by the formula (3), and the compound represented by the formula (4) is used in an amount of 2.0 moles per mole, and if necessary, an acid catalyst is used as a condensation accelerator of 0.001 to 2.0 moles. It is 0.01 to 1.0 mol, and is stirred in a polar solvent such as water or alcohol at a normal pressure of 0.0 to 100 ° C for about 10 minutes to 24 hours to carry out a reaction. Further, after the reaction, the object can be purified by a known method. For example, it is cooled by ice water to precipitate crystals and separate to obtain a crude crystal.

The ratio of the compound represented by the formula (3) to the compound represented by the formula (4) is preferably 1.0:2.0 to 1.0:100, more preferably 1.0:2.0 to 1.0:10, in terms of a molar ratio. The reaction can be carried out at room temperature, and if necessary, at a high temperature, and it is preferably carried out at a temperature of from 0.0 to 100 ° C, more preferably from about 20 to 80 ° C, in consideration of the boiling point of the raw material carbonyl compound.

The gas environment in which the reaction is carried out may be in an air gas atmosphere or in a passive gas atmosphere such as nitrogen or argon.

The reaction pressure is preferably carried out under atmospheric pressure in terms of economy, but it can also be carried out under high pressure or under reduced pressure.

The pH in the reaction system may be neutral, but if the above acid is used as the condensation accelerator, the reaction proceeds rapidly, which is preferred.

The polar solvent is not particularly limited, and examples thereof include water, methanol, ethanol, propanol, isopropanol, butanol, and isobutanol. It is also possible to use a carbonyl compound which is a raw material, that is, acetone, methyl ethyl ketone, diethyl ketone, isopropanal, methyl isopropanone, methyl isobutyl ketone, 2-pentanone, 2-hexanone, 2-heptanone, Formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, acrolein, methacrolein, crotonaldehyde, benzalacetone, and the like. Aqueous solvents are preferred in view of economics.

The condensation accelerator is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, acetic acid, p-toluenesulfonic acid, nitric acid, oxalic acid, phosphoric acid, hydrobromic acid, hydroiodic acid, aminesulfonic acid, and perchloric acid. It is preferred to use the same acid as the acid of the raw material diamine sulfonium salt.

After the completion of the reaction, the crystals are precipitated by a cooling operation or the like, and the obtained crystals are separated by filtration, washed with water, alcohol or the like, and then dried under reduced pressure to obtain a compound of the present embodiment.

When the crystal is not precipitated after the completion of the reaction and is a homogeneous solution, for example, the crystal can be precipitated by the following method. A carbonate such as sodium carbonate or sodium hydrogencarbonate or a weakly basic aqueous solution containing such a salt is added to the homogeneous reaction solution to precipitate crystals of the bisalkylenediamine fluorene or its carbonate. The compound of the present embodiment can be obtained by subjecting it to filtration and carrying out the same operation as above.

Most of the product obtained by the operation of adding an aqueous solution containing the above carbonate forms a salt with carbonic acid, but depending on the kind of the carbonyl compound to be used, a bis-alkylenediamine fluorene which does not form a salt is sometimes unexpectedly obtained. The carbonyl compound which can obtain a bis-alkylenediamine oxime which does not form a salt is not particularly limited, and examples thereof include acrolein, isobutyraldehyde, and benzalacetone, and the like, as a bisalkylenediamine fluorene carbonate is obtained. The carbonyl compound is not particularly limited, and examples thereof include methacrolein and crotonaldehyde.

When the compound represented by the formula (1) or the formula (2) of the present embodiment has a bis-alkylenediamine fluorene skeleton, it can be identified by ¹ H-NMR, whether or not a salt is formed with an acid, and can be identified by elemental analysis.

When the compound represented by the formula (1) or the formula (2) of the present embodiment is used as a rubber additive, the low loss property of the vulcanized rubber composition containing an inorganic filler such as cerium oxide and the viewpoint of improving the tensile breaking strength are considered. The melting point is preferably 50 to 300 ° C, and more preferably 50 to 200 ° C. When the melting point is 50 to 300 ° C, it is solid at normal temperature, so workability is good. When the temperature is 50 to 200 ° C, it is melted at the kneading temperature of the rubber or the vulcanization temperature, and tends to be easily mixed with the rubber.

<Modified rubber> The modified rubber (A) (hereinafter also referred to as "modified rubber") of the present embodiment is selected from at least one selected from the group consisting of natural rubber and synthetic rubber (hereinafter referred to as "raw rubber", also referred to as "rubber" or "raw material", is modified by a compound represented by formula (1) or formula (2) (hereinafter also referred to as "rubber modifier" or "modifier"). obtain. When the modified rubber (A) of the present embodiment is used as a rubber composition containing an inorganic filler such as cerium oxide, it is possible to exhibit an excellent effect on low loss, breaking strength, and the like.

The raw material rubber of the modified rubber (A) of the present embodiment may be either natural rubber or synthetic rubber, or both of them, and in particular, when natural rubber is used, the effect of the embodiment can be remarkably obtained, which is preferable. The synthetic rubber is a synthetic rubber which is improved in affinity with an inorganic filler by end-modification by a polar group as disclosed in Patent Document 3, or a single one containing a polar group as disclosed in Patent Document 4. The synthetic rubber which is copolymerized to improve the affinity with the inorganic filler can easily introduce a polar group during polymerization, and the natural rubber cannot be used in such a manner.

The natural rubber is not particularly limited, and any shape of the sheet rubber or the block rubber obtained by solidifying and drying the natural rubber latex can be used as a raw material. As a sheet-like rubber, a smog film (Ribbed) obtained by grading the film by using smoked smoke according to the classification of the "International Quality Packaging Standard for Various Grades of Natural Rubber" (collectively referred to as the Green Paper) can be cited. Smoked Sheet (RSS), Air Dry Sheet (ADS) obtained by subjecting the film to hot air drying, Crepe which fully washes the coagulum and dried by hot air, and the like, and TC rubber ( Technically Classified Rubber), SP (Super Processing Rubber), MG rubber, PP silicone, rubber with added softener and Peptizer. The block rubber is not particularly limited, and examples thereof include SMR (Standard Malaysian Rubber) in Malaysia, SIR in Indonesia, TTR in Thailand, SCR in Sri Lanka, and SSR in Singapore. These natural rubber raw materials can be used alone or in combination of two or more.

Further, a rubber obtained by oxidizing a natural rubber latex may be used, and oxidation of the natural rubber latex can be carried out by a known method. For example, a natural rubber latex can be obtained by performing air oxidation in the presence of a metal-based oxidation catalyst by dissolving a natural rubber latex dissolved in an organic solvent at a ratio of 1.0 to 30% by mass in accordance with JP-A-H08-81505. Oxidation. Further, for example, the carbonyl compound may be added to the natural rubber latex to perform oxidation as described in JP-A-9-136903. In order to promote air oxidation, air oxidation may be performed in the presence of a radical generating agent, as described in Japanese Laid-Open Patent Publication No. Hei 9-136903. The radical generating agent is not particularly limited, and examples thereof include a peroxide radical generating agent, a redox radical generating agent, and an azo radical generating agent.

The synthetic rubber which can be used as a raw material of the modified rubber (A) is not particularly limited, and examples thereof include 1,4-polybutadiene, 1,2-polybutadiene, and 1,4-polyisoprene, and 3 , 4-polyisoprene, styrene-butadiene rubber, terminal modified styrene butadiene rubber, chloroprene rubber, nitrile rubber, ethylene-propylene rubber, ethylene propylene diene rubber (Ethylene Propylene) Diene Rubber) is a diene rubber or the like having a double bond in a molecule.

In the present embodiment, the above-described natural rubber, modified rubber, or both may be used. In other words, one type of these may be used alone or two or more types may be used in combination.

The rubber modifier of the present embodiment is a compound represented by the above formula (1) or (2) (hereinafter also referred to as "bisalkylenediamine sulfonium salt" or "bisalkylenediamine oxime". .). 【化28】 In the formula, X is an acid which forms a salt with a hydrazine moiety, and R ¹ and R ² are each independently selected from an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, and an alkenyl group ( Each of the groups includes at least one selected from the group consisting of one or more substituents containing a sulfur atom, a nitrogen atom or an oxygen atom, and a hydrogen atom; In the formula, R ¹ and R ² are each independently selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, and an alkenyl group (all of which include one or more). At least one of the group consisting of a sulfur atom, a nitrogen atom, or a substituent of an oxygen atom, and a hydrogen atom.

When the modified rubber of the present embodiment is used for a rubber composition, the factors of excellent low loss are presumably as follows (however, it is not limited thereto). The modified rubber obtained by reacting the above modifier with the rubber is derived from the hydrazine moiety of the modifier and the rubber bond. Since the modified rubber has a polar group such as an amine group, and the polar group of the inorganic filler, especially cerium oxide, the affinity between the sterol groups on the surface of the cerium oxide is increased, whereby the rubber-inorganic filler is densely bonded. When the rubber molded body such as a tire is obtained, the rubber molded article having excellent low loss is obtained. In particular, the ruthenium portion derived from the modifier acts as a polar group of the modified rubber to form a strong hydrogen bond with the sterol group on the surface of the cerium oxide, thereby contributing to improvement of the adhesion between the rubber-inorganic filler. The formation of this strong hydrogen bond is caused by the height of the polarity of the crucible portion, the strength of the alkali, and the like.

On the other hand, the alkylene moiety of the bisalkylenediamine sulfonium salt or the bisalkylenediamine guanidine is presumed to have a function of controlling the reactivity of the hydrazine moiety (melamine group) present in the molecule. (However, not limited to this factor). That is, the alkylene group of the bisalkylenediamine sulfonium salt or the bisalkylenediamine oxime and the rubber are less reactive than those without the alkylene group, so when the rubber and the inorganic filler are mixed, It can suppress the increase in rubber viscosity and improve the processability.

Next, the manufacturing method of the modified rubber of the present embodiment will be described. The modified rubber of the present embodiment is obtained by mixing a compound represented by the formula (1) or the formula (2) and a rubber by a mixer, an extruder, a kneader or the like. Considering the idea of improved dispersibility, it is better to mix with a kneading machine. As a method of adding a compound represented by the formula (1) or the formula (2) to a mixer, an extruder, a kneader or the like, any of the following methods may be used: a method of directly adding a powder, and dissolving it The method of adding the solvent as a solution, and adding it as an emulsion solution.

In order to obtain the reaction conditions of the modified rubber of the present embodiment, the rubber and the modifier are preferably mixed at a temperature of 20 to 180 ° C and modified, and mixed at a temperature of 50 to 160 ° C. Better modification. If it is a temperature of 20 ° C to 180 ° C, the rubber and the modifier can be sufficiently mixed, and the tendency of the decomposition of the modifier can be suppressed. The mixing time of the rubber should be adjusted to 0.5 to 30 minutes at the above reaction temperature, preferably 2.0 to 10 minutes. When it is 0.5 to 30 minutes, there is a tendency that the rubber and the modifier can be sufficiently reacted without causing productivity. The gaseous environment of the reaction is preferably carried out in the presence of oxygen in the presence of air. The reason is that there is a tendency that the rubber is partially oxidized and the reactivity with the modifier is improved by kneading in the presence of oxygen.

Further, the modified rubber of the present embodiment can be obtained by mixing a modifier with a rubber at a time such as an extruder or a kneading machine, but a method of oxidizing the natural rubber latex and solidifying the rubber is used. Or using an applied mechanical force called mastication to the raw material rubber before the addition of the modifier, loosening the molecular association (association), and cutting the molecular chain to adjust the rubber plasticity to A method which is easy to process, and which also improves the reactivity of the modifier with the rubber, is also desirable. A debonding agent (Peptizer) can also be used in the above mastication step.

Further, even in the modifier, the rubber, the inorganic filler, and the decane coupling agent, various blending agents appropriately selected as needed are blended, and mixed using a mixer, an extruder, a kneader, or the like. A modified rubber is still partially formed in the rubber composition. This method is more preferable than the above-described method of mixing the modifier and the rubber. When this operation is carried out, the rubber composition of this embodiment can be obtained.

When the amount of the modifier used in the production of the modified rubber of the present embodiment is considered, it is considered that the modified rubber is uniformly introduced into a small amount of a polar group in each molecule of the rubber, and the workability is improved without lowering the workability. The affinity of the filler such as ruthenium or carbon black, and the rubber composition excellent in low loss, and the total amount of the rubber (100% by mass) is preferably 0.01 to 10% by mass, and 0.1 to 3% by mass. good.

<Rubber Composition> The rubber composition of the present embodiment contains a modified rubber (A), a filler containing the inorganic filler (B), and a decane coupling agent (C).

The rubber composition of the present embodiment is obtained by mixing a modified rubber (A), a filler containing the inorganic filler (B), and a decane coupling agent (C). Further, the rubber composition of the present embodiment is a modified rubber (A) obtained by mixing a modifier, a raw material rubber, a filler containing the inorganic filler (B), and a decane coupling agent (C). The rubber composition is also acceptable. Further, the temperature at the time of mixing is preferably in the range of 20 to 180 ° C, and the range of 50 to 160 ° C is more preferable. Further, in the mixing, the amount of the modifier used is preferably 0.01 to 10% by mass, more preferably 0.1 to 3.0% by mass, based on the total amount (100% by mass) of the raw material rubber.

The inorganic filler (B) of the present embodiment refers to an inorganic material containing at least one selected from the group consisting of an oxide or a hydroxide of a cerium, a typical metal or a transition metal, a hydrate thereof, and a carbonate of the metal. Compound.

The inorganic filler (B) is not particularly limited as long as it is an inorganic filler used in the technical field. Further, the carbon black to be described later is not included in the inorganic filler (B) referred to herein, and does not conform to the inorganic filler (B). Inorganic fillers are roughly classified into reinforcing fillers such as active cerium oxide, surface-treated clay, and non-reinforcing fillers such as calcium carbonate, clay, and talc. Specific examples of the inorganic filler (B) include cerium oxide, calcium carbonate, magnesium carbonate, aluminum oxide, aluminum hydroxide, aluminum silicate (clay), magnesium ruthenate (talc), calcium citrate, zinc, and the like. . If the interaction with the modified rubber is considered, the reinforcing filler is preferred, and the cerium oxide is more preferable. The cerium oxide is not particularly limited, and wet cerium oxide (aqueous ceric acid), dry cerium oxide (anhydrous ceric acid), or the like can be used.

When cerium oxide is used, the BET specific surface area is preferably from 40 to 350 m ² /g. When the BET specific surface area of cerium oxide is within this range, the particle size of cerium oxide is appropriate, the tensile strength is improved, and the hysteresis loss tends to decrease. The BET specific surface area can be measured in accordance with JIS Z8830:2013.

In addition to the inorganic filler (B) described above, the filler used in the rubber composition of the present embodiment may be added with carbon black in order to enhance the reinforcing effect. That is, the above filler material includes carbon black. Further, the carbon black and the inorganic filler (B) are different filler materials, and are clearly distinguished from the inorganic filler (B). Examples of the carbon black include those of various grades such as GPF, FEF, SRF, HAF, ISAF, and SAF.

The total content of the inorganic filler (B) and the carbon black of the rubber composition of the present embodiment is not particularly limited, and the workability is not deteriorated, and the content of the sufficiently low loss effect or the reinforcing effect can be obtained with respect to the raw material rubber 100. The mass fraction is preferably in the range of 5.0 to 100 parts by mass, and the range of 20 to 80 parts by mass is more preferable.

The decane coupling agent (C) of the present embodiment is not particularly limited, and examples thereof include bis(3-triethoxydecylpropyl)tetrasulfide and bis(3-trimethoxydecylpropyl)tetrasulfide. , bis(3-methyldimethoxydecylpropyl) tetrasulfide, bis(2-triethoxydecylethyl)tetrasulfide, bis(3-triethoxydecylpropyl) Disulfide, bis(3-trimethoxydecylpropyl) disulfide, bis(3-triethoxydecylpropyl)trisulfide, 3-hexylthiopropyltriethoxydecane , 3-octylthiopropyltriethoxydecane, 3-hexylthiopropyltriethoxydecane, 3-laurylthiopropyltriethoxydecane, 2-hexylsulfonylethyl Ethoxy decane, 2-octyl thioethyl triethoxy decane, 2-hexyl thioethyl triethoxy decane, 2-lauryl thioethyl triethoxy decane, 3-hexyl decyl Thiopropyltrimethoxydecane, 3-octylthiopropyltrimethoxydecane, 3-hexylthiopropyltrimethoxydecane, 3-laurylthiopropyltrimethoxydecane, 2-hexyldecyl Thioethyltrimethoxydecane, 2-octylthioethyltrimethoxydecane, 2-hexylthioethyltrimethyl Oxydecane, 2-laurylthioethyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropylmethyldimethoxydecane , 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldi Ethoxy decane, 3-trimethoxydecyl propyl-N,N-dimethylthiocarbamyl fluorenyl tetrasulfide, 3-trimethoxydecyl propyl benzothiazolyl tetrasulfide, 3- Trimethoxymercaptopropyl methacryl fluorenyl monosulfide or the like. The content thereof is preferably from 1 to 20 parts by mass based on 100 parts by mass of the inorganic filler.

In addition to the above-mentioned modified rubber, rubber, and inorganic filler, the rubber composition of the present embodiment is not particularly limited as long as it is used in the rubber industry, and can be appropriately selected within the scope of the object of the present embodiment. And blending anti-aging agent, softener, vulcanization accelerator, vulcanization accelerator, vulcanizing agent, etc. Commercially available products can be suitably used as such a blending agent.

The type of the anti-aging agent is not particularly limited, and examples thereof include naphthylamine, p-phenylenediamine, hydroquinone derivatives, bis, ginseng, polyphenol, diphenylamine, quinoline, and monophenol. A thiodiamine-based or a diphenylamine-based amine-based anti-aging agent is preferred from the viewpoint of further anti-aging effects from the viewpoint of further anti-aging effects. The diphenylamine-based anti-aging agent is not particularly limited, and examples thereof include 4,4′-(α-methylbenzyl)diphenylamine and 4,4′-(α,α-dimethylbenzyl)diphenylamine. P-(p-toluene-sulfonylamino)diphenylamine, 4,4'-dioctyldiphenylamine, and the like. Among these, 4,4'-(?-methylbenzyl)diphenylamine is more preferable from the viewpoint of further high anti-aging effect. Further, examples of the p-phenylenediamine-based anti-aging agent include N,N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, and N,N. '-Di-2-naphthyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-phenyl-N'-(3-methylpropenyloxy-2- Hydroxypropyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-benzene Diamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-benzene Diamine and the like. Among these, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine is more preferable from the viewpoint of further high anti-aging effect and cost. The content of the anti-aging agent in the rubber composition is preferably 0.1 to 5% by mass based on the rubber component in the rubber composition.

The type of the softening agent is not particularly limited, and examples thereof include mineral oil-based softeners derived from petroleum and coal tar, and vegetable oil-based softeners derived from fatty oils and pines, and synthetic resin-based softeners.

The type of the vulcanization accelerator is not particularly limited, and examples thereof include a thiazole series such as Mercaptobenzothiazole and 2,2'-dibenzothiazolyl disulfide; and N-cyclohexyl-2-benzothiazolyl Sulfonamide, N,N'-dicyclohexyl-2-benzothiazolylsulfenamide, N'-tertiary butyl-2-benzothiazolylsulfenamide, and the like. A phenyl group or the like. These vulcanization accelerators may be used alone or in combination of two or more. The content thereof is preferably 0.1 to 5.0 parts by mass based on 100 parts by mass of the rubber component. The vulcanization accelerating aid is not particularly limited, and examples thereof include stearic acid and zinc hydride.

The type of the vulcanizing agent is not particularly limited, and those commonly used in the technical field can be suitably used, and examples thereof include sulfur and peroxide. These should be sulfur. The content of the vulcanizing agent is preferably 0.1 to 5.0 parts by mass, more preferably 0.5 to 3.0 parts by mass, per 100 parts by mass of the rubber component. When the content of the vulcanizing agent is 0.1 part by mass or more, sufficient vulcanization tends to be obtained, and the content of the vulcanizing agent is 5.0 parts by mass or less, so that the coking time does not become short, and rubber such as kneading can be effectively suppressed. The problem of burning.

<Tire> The tire of the present embodiment is characterized in that the above-described rubber composition is used, and it is particularly preferable to use the rubber composition as a tread of a tire member. The rubber composition described above is used for a tire of a tread, and is excellent in low fuel cost. Further, the tire of the present embodiment is not particularly limited, except that the rubber composition is used for any tire member, and can be produced according to a conventional method. Further, as the gas to be filled in the tire, in addition to normal air or air whose oxygen partial pressure is adjusted, a passive gas such as nitrogen gas, argon gas or helium gas can be used.

When the modified rubber of the present embodiment is a rubber composition containing an inorganic filler such as cerium oxide and a tire using the same, excellent low loss and breaking strength can be obtained. [Examples]

The invention is illustrated in more detail in the following examples, but the invention is not limited to the following examples.

(Example 1) Synthesis of bis(1,2-dimethylpropylene)diamine hydrazine hydrochloride (5) [Chem. 30] To a 50 mL eggplant type flask, 783 mg of diamine hydrazine hydrochloride (6.2 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), water 6 mL, and 0.25 mL of 12N hydrochloric acid were added, and the mixture was stirred at room temperature for 10 minutes, and then methyl isopropanone was added. 1.102 g (12.8 mmol) was stirred at room temperature using a magnetic stir bar. After stirring, white crystals were precipitated, and after stirring for 2 hours, the crystals were separated by filtration. After washing with water, it was dried under vacuum at 50 ° C for 22 hours to give 445 mg (1.7 mmol) as a white solid. The solid obtained in the ¹ H-NMR analysis, it was confirmed as bis (1,2-dimethylpropylene) guanidine hydrochloride diamine ^{(1 H-NMR (DMSO-} d6,500MHz, δ; ppm) = 2.6-2.5 (m; 2H), 1.9 (s; 6H), 1.1 (dd; 12H)). The molar yield was 27%. In addition, the melting point was measured by a micro melting point measuring device BY-1 (manufactured by Yazawa Scientific Co., Ltd.), and it was 144-145 ° C, and it was carried out using a carbon, hydrogen, and nitrogen simultaneous quantitative apparatus CHNCoder MT-6 (Yanaco Analytical Industry Co., Ltd.). Elemental analysis, the results are calculated as: C, 50.47; H, 9.24; N, 26.75, relative to this, measured 値: C, 49.84; H, 9.43; N, 26.98.

(Example 2) Synthesis of bis(1-methylpentylene)diamine hydrazine hydrochloride (6) [Chem. 31] To a 50 mL eggplant type flask, 759 mg (6.0 mmol) of diamine hydrazine hydrochloride, 6 mL of water, and 0.25 mL of 12N hydrochloric acid were added, and the mixture was stirred at room temperature for 10 minutes, then 1.12 g (12.1 mmol) of 2-hexanone was added, using magnetic stirring. The mixture was stirred at room temperature. White crystals were precipitated during the stirring, and after stirring for 2 hours, the crystals were separated by filtration. After washing with water, it was dried under vacuum at 50 ° C for 16 hours to give white solid (1. The solid obtained in the ¹ H- NMR analysis, it was confirmed as bis (1-methyl-pentyl) guanidine hydrochloride diamine ^{(1 H-NMR (DMSO-} d6,500 MHz, δ; ppm) = 0.9 ( m; 6H), 1.2-1.3 (m; 4H), 1.4-1.5 (m; 4H), 2.0 (s; 6H), 2.3 (t; 4H), 8.0-8.2 (br)). The molar yield was 68%. In addition, the melting point was measured using a micro melting point measuring device BY-1 (manufactured by Yazawa Scientific Co., Ltd.), and as a result, it was 100-101 ° C, and a carbon, hydrogen, and nitrogen simultaneous metering device CHNCoder MT-6 (Yanaco Analytical Industry Co., Ltd.) was used. Elemental analysis was carried out and the results were calculated as: C, 53.87; H, 9.74; N, 24.16. In contrast, measured 値: C, 53.46; H, 10.03; N, 24.31.

(Example 3) Synthesis of bis(1-methylhexylidene)diamine hydrazine hydrochloride (7) [Chem. 32] To a 50 mL eggplant type flask, 741 mg (5.9 mmol) of diamine hydrazine hydrochloride, 6 mL of water, and 0.25 mL of 12N hydrochloric acid were added, and the mixture was stirred at room temperature for 10 minutes, and then 1.17 g (12.0 mmol) of 2-heptanone was added, and magnetic properties were used. The stirrer was stirred at room temperature. White crystals were precipitated during the stirring, and after stirring for 2 hours, the crystals were separated by filtration. After washing with water and hexane, it was dried under vacuum at 50 ° C for 15 hours to give 1.51 g (4.8 mmol) of white solid. In ¹ H-NMR analysis of the solid obtained, identified as bis (1-methyl-hexyl) guanidine hydrochloride diamine ^{(1 H-NMR (DMSO-} d6,500MHz, δ; ppm) = 0.9 (t; 6H ), 1.2-1.3 (m; 8H), 1.5-1.6 (m; 4H), 1.9 (s; 6H), 2.3 (t; 4H), 8.1 (br)). The molar yield was 81%. In addition, the melting point was measured by a micro melting point measuring instrument BY-1 (manufactured by Yazawa Scientific Co., Ltd.), and it was 100-102 ° C, and it was carried out using a carbon, hydrogen, and nitrogen simultaneous quantitative apparatus CHNCoder MT-6 (Yanaco Analytical Industry Co., Ltd.). Elemental analysis, the results are calculated as: C, 56.67; H, 10.15; N, 22.03, relative to this, measured 値: C, 56.74; H, 10.60; N, 22.10.

(Example 4) Synthesis of bis(2-methylallyl)diamine sulfonium carbonate (8) [Chem. 33] To a 50 mL eggplant type flask, 1.50 g (11.9 mmol) of diamine hydrazine hydrochloride, 12 mL of water, and 0.1 mL of 12N hydrochloric acid were added, and the mixture was stirred at room temperature for 10 minutes, and then 1.80 g (25.7 mmol) of methacrolein was added. The stirrer was stirred at room temperature. Crystals were precipitated during the stirring, and after stirring for 1 hour, 20 mL of a saturated aqueous sodium hydrogencarbonate solution was added to the mixture. The precipitated crystals were separated, washed with water and dried at 50 ° C for 20 hr to afford 922 mg ( 3.6 mmol) of white solid. In ¹ H-NMR analysis of the solid obtained, identified as bis (2-methylsulfinyl-allyl) diamino guanidine carbonate ^{(1 H-NMR (DMSO-} d6,500MHz, δ; ppm) = 2.0 (s; 6H), 5.5 (s; 2H), 5.6 (s; 2H), 8.1 (s; 2H), 8.2 (br)). The molar yield was 30%. Further, the melting point was measured using a micro melting point measuring instrument BY-1 (manufactured by Yazawa Scientific Co., Ltd.), and no melting point was observed. Elemental analysis was carried out using CHNCoder MT-6 (Yanaco Analytical Industry Co., Ltd.), which is a carbon, hydrogen, and nitrogen simultaneous metering device. The result is 値: C, 47.05; H, 6.71; N, 27.43. In contrast, the actual measurement 値: C , 45.60; H, 7.22; N, 29.54.

(Example 5) Synthesis of bis(3-methylallyl)diamine sulfonium carbonate (9) [Chem. 34] 1.51 g (12.0 mmol) of diamine hydrazine hydrochloride, 12 mL of water, and 0.1 mL of 12N hydrochloric acid were added to a 50 mL eggplant type flask, and the mixture was stirred at room temperature for 10 minutes, and then 1.75 g (25.0 mmol) of crotonaldehyde was added, and magnetic stirring was used. The mixture was stirred at room temperature. Crystals were precipitated during stirring, and after stirring for 1 hour, 20 mL of water was added to the reaction liquid. The precipitated crystals were separated, washed with water and dried at 50 &lt;0&gt;C for 20 hours under vacuum to afford 919 mg ( 3.6 mmol). In ¹ H-NMR analysis of the solid obtained, identified as bis (3-allyl-methylsulfinyl) diamino guanidine carbonate ^{(1 H-NMR (DMSO-} d6,500MHz, δ; ppm) = 1.9 (d; 6H), 6.2 (m; 2H), 6.3 (m; 2H), 8.0 (d; 2H), 8.1 (s; 2H), 11.8-12.0 (br)). The molar yield was 30%. In addition, the melting point was measured by a micro melting point measuring device BY-1 (manufactured by Yazawa Scientific Co., Ltd.), and it was 168-169 ° C, and it was carried out using a carbon, hydrogen, and nitrogen simultaneous quantitative apparatus CHNCoder MT-6 (Yanaco Analytical Industry Co., Ltd.). Elemental analysis, the results are calculated as: C, 47.05; H, 6.71; N, 27.43, relative to this, measured 値C, 46.48; H, 7.10; N, 30.09.

(Example 6) Synthesis of bis(1-methyl-3-phenylallyl)diamine hydrazine hydrochloride (10) [Chem. 35] To a 50 mL eggplant type flask, 752 mg (6.0 mmol) of diamine hydrazine hydrochloride, 6 mL of methanol, and 0.25 mL of 12N hydrochloric acid were added, and the mixture was stirred at room temperature for 10 minutes, and then 1.633 g (11.2 mmol) of benzylideneacetone was added, and magnetic stirring was used. The mixture was stirred at room temperature. Immediately after the start of the stirring, yellow crystals were precipitated, and after stirring for 2 hours, the crystals were separated by filtration, washed with water, and then dried at 50 ° C for 17 hours under vacuum to obtain 1.94 g (5.1 mmol) as a yellow solid. In ¹ H-NMR analysis of the solid obtained, identified as bis (1-methyl-3-phenyl-allyl) guanidine hydrochloride diamine ^{(1 H-NMR (DMSO-} d6,500MHz, δ; ppm ) = 2.2 (s; 6H), 7.0 (d; 2H), 7.3 (d; 2H), 7.3 (t; 2H), 7.4 (t; 4H), 7.6 (d; 4H), 8.5-8.6 (br) 11.6-11.7(br)). The molar yield was 85%. In addition, the melting point was measured using a micro melting point measuring device BY-1 (manufactured by Yazawa Scientific Co., Ltd.), and it was 263-265 ° C, and it was carried out using a carbon, hydrogen, and nitrogen simultaneous quantitative apparatus CHNCoder MT-6 (Yanaco Analytical Industry Co., Ltd.). Elemental analysis, the results are calculated as: C, 64.85; H, 6.18; N, 17.19, relative to this, measured 値: C, 66.04; H, 6.33; N, 18.34.

(Example 7) Synthesis of bis(2-methylpropylene)diamine hydrazine (11) [Chem. 36] To a 50 mL eggplant type flask, 741 mg (5.9 mmol) of diamine hydrazine hydrochloride, 6 mL of methanol, and 0.25 mL of 12N hydrochloric acid were added thereto, and the mixture was stirred at room temperature for 10 minutes, and then 861 mg (11.9 mmol) of isobutyraldehyde was added thereto, using a magnetic stir bar. Stir at room temperature. After stirring for 2 hours, 20 mL of a saturated aqueous sodium hydrogencarbonate solution was added to the mixture. The precipitated crystals were separated, washed with water and dried at 50 &lt;0&gt;C for 15 hrs to afford 321 mg (1.6 mmol). The solid obtained by ¹ H-NMR analysis was confirmed to be bis(2-methylpropylidene)diamine hydrazide. ^{1 H-NMR (DMSO-d6,500MHz} , δ; ppm) = 1.0 (dd; 12H), 2.4-2.5 (m; 2H), 5.8 (s; 2H), 7.2 (dd; 2H), 9.8 (br) ). The molar yield was 28%. In addition, the melting point was measured by a micro melting point measuring instrument BY-1 (manufactured by Yazawa Scientific Co., Ltd.), and it was 65-67 ° C, and it was carried out using a carbon, hydrogen, and nitrogen simultaneous quantitative apparatus CHNCoder MT-6 (Yanaco Analytical Industry Co., Ltd.). Elemental analysis, the result is calculated as: C, 54.79; H, 9.71; N, 35.50. In contrast, the measured enthalpy is C, 54.56; H, 10.02; N, 35.07.

(Example 8) Synthesis of bis-allyldiamine hydrazide (12) [Chem. 37] To a 50 mL eggplant type flask, 754 mg (6.0 mmol) of diamine hydrazine hydrochloride, 6 mL of water, and 0.05 mL of 12N hydrochloric acid were added, and the mixture was stirred at room temperature for 10 minutes, and then 1.01 g (18.0 mmol) of acrolein was added thereto, using a magnetic stir bar. Stir at room temperature. After 1 hour from the start of the stirring, crystals were precipitated, and after stirring for 4 hours, 20 mL of a saturated aqueous sodium hydrogencarbonate solution was added to the mixture. The precipitated crystals were separated by filtration, washed with water and dried at 50 ° C for 20 hr to afford 331 mg (2.0 mmol) of white solid. The solid obtained by ¹ H-NMR analysis was confirmed to be bis-allyldiamine hydrazide ( ¹ H-NMR (DMSO-d6, 500 MHz, δ; ppm) = 5.4 (d; 2H), 5.5 (d; 2H ), 6.5 (ddd; 2H), 6.0-6.3 (br), 7.7 (d; 2H)). The molar yield was 33%. In addition, the melting point was measured by a micro melting point measuring device BY-1 (manufactured by Yazawa Scientific Co., Ltd.), and it was 149-152 ° C, and it was carried out using a carbon, hydrogen, and nitrogen simultaneous quantitative apparatus CHNCoder MT-6 (Yanaco Analytical Industry Co., Ltd.). Elemental analysis, the results are calculated as: C, 50.89; H, 6.71; N, 42.39, relative to this, measured 値: C, 50.03; H, 6.68; N, 41.27. The temperature at the time when the heating peak portion due to polymerization started to rise was determined by a differential scanning calorimeter (DSC 6220, manufactured by Seiko Instruments Inc., 10 ° C/min) as a result of the polymerization initiation temperature of 150 ° C.

(Example 9) Synthesis of bis(1-methyl-3-phenylallyl)diamine hydrazide (13) [Chem. 38] To a 50 mL eggplant type flask, 754 mg (6.0 mmol) of diamine hydrazine hydrochloride, 6 mL of methanol, and 0.25 mL of 12N hydrochloric acid were added, and the mixture was stirred at room temperature for 10 minutes, then 1.79 g (12.2 mmol) of benzylideneacetone was added, and magnetic stirring was used. The mixture was stirred at room temperature. Immediately after the start of the stirring, yellow crystals were precipitated, and after stirring for 2 hours, 20 mL of a saturated aqueous sodium hydrogencarbonate solution was added to the mixture. The precipitated crystals were separated, washed with water, and then dried at 50 ° C for 15 hr. to afford 1.73 g (5.0 mmol) as a yellow solid. The solid obtained by ¹ H-NMR analysis was confirmed to be bis(1-methyl-3-phenylallyl)diamine hydrazide ( ¹ H-NMR (ACETONE-d6, 500 MHz, δ; ppm) = 2.2 (s; 6H), 6.9-7.1 (m; 4H), 7.3 (t; 2H), 7.4 (t; 4H), 7.6 (d; 4H)). The molar yield was 83%. In addition, the melting point was measured by a micro melting point measuring instrument BY-1 (manufactured by Yazawa Scientific Co., Ltd.), and it was 81-83 ° C and 160-163 ° C, and a carbon, hydrogen, and nitrogen simultaneous metering device CHNCoder MT-6 (Yanaco analysis industry) was used. (Unit)) Elemental analysis was carried out and the results were calculated as: C, 73.02; H, 6.71; N, 20.27, relative to this, measured 値: C, 71.57; H, 8.98; N, 19.54.

(Example 10) Synthesis of bis(1-methylpropylene)diamine hydrazine hydrochloride (14) [Chem. 39] To a 100 mL eggplant type flask, 3.019 g (24 mmol) of diamine hydrazine hydrochloride, 12 mL of water, and 0.1 mL of 12N hydrochloric acid were added, and the mixture was stirred at room temperature for 10 minutes, and then methyl ethyl ketone (4.087 g (57 mmol) was added, using a magnetic stirrer at room temperature. Stir. Immediately after the start of stirring, white crystals were obtained. After stirring for 0.5 hour, the reaction liquid was filtered, washed with water and dried at 50 ° C for 16 hours under vacuum to obtain white crystals 4.41 g (19 mmol). In ¹ H-NMR analysis of the solid obtained, identified as bis (1-methyl-propyl) guanidine hydrochloride diamine ^{(1 H-NMR (DMSO-} d6,500 MHz, δ; ppm) = 1.1 (t ; 6H), 2.0 (s; 6H), 2.3 (q; 4H)). The molar yield was 79%. In addition, the melting point was measured by a micro melting point measuring device BY-1 (manufactured by Yazawa Scientific Co., Ltd.), and it was 133-134 ° C, and it was carried out using a carbon, hydrogen, and nitrogen simultaneous quantitative apparatus CHNCoder MT-6 (Yanaco Analytical Industry Co., Ltd.). Elemental analysis, the results are calculated as: C, 46.25; H, 8.62; N, 29.96. In contrast, the measured enthalpy is C, 46.02; H, 9.05; N, 29.98.

(Example 11) In a Laboplastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) which was heated to 30 ° C in a mixer, 41.4 g of a natural rubber solidified body (RSS #1, manufactured by Kato Co., Ltd.) was charged at a rotation speed. 60 rpm was kneaded in the closed state for 1 minute, and kneaded in the open state for 4 minutes. When the rubber temperature was raised to 80 ° C, the bis(1-methylpropylene)diamine hydrazine hydrochloride obtained in Example 10 was added to 0.414 g (1.77 mmol), and kneaded for 3 minutes. Thereby, the modified rubber 1 was obtained. At this time, the rubber temperature reached 85 °C.

The modified rubber 1 (9.0 g) was heated and refluxed in 200 g of a 2:1 mixed solvent of acetone and methanol for 2 hours to carry out extraction of unreacted 1,3-diaminoguanidine hydrochloride. After distilling off the solvent under reduced pressure, the residue was quantitatively analyzed by liquid chromatography to give bis(1-methylpropylidene)diamine hydrazide hydrochloride: 0.0048 g (0.021 mmol). The base is diamine hydrazine hydrochloride 0.0047 g (0.023 mmol, 0.0053 g if converted to bis(1-methylpropylene)diamine hydrazine hydrochloride). That is, the total amount of unreacted bis(1-methylpropylene)aminoguanidine hydrochloride was 0.0101 g (0.043 mmol). The bis(1-methylpropylene)diamine hydrazine hydrochloride contained in the modified rubber 1 (9.0 g) before the elution was 0.0891 g (0.381 mmol), and the added diamine hydrazine hydrochloride was 89 mol% has reacted with natural rubber.

Therefore, it was confirmed that the addition amount of the bis(1-methylpropylene)diamine hydrazine of the modified rubber 1 was 0.1% by mass based on the solid rubber component in the natural rubber raw material.

(Reference Example 1) 41.4 g of a natural rubber solidified body (RSS #1) was placed in a Laboplastomill heated to 30 ° C in a mixer, and kneaded in a closed state at a rotation speed of 60 rpm for 1 minute, and kneaded in a lid-opening state for 4 minutes. After the rubber temperature reached 80 ° C due to shear heat, it was further kneaded for 3 minutes, whereby unmodified rubber 1 was obtained. At this time, the rubber temperature reached 85 °C.

(Example 12, Comparative Example 1) According to the composition of Table 1, the modified rubber 1 or the unmodified rubber 1, the ceria, the decane coupling agent, the zinc hydride, and the stearic acid were firstly dried at 140 ° C with the above Laboplastomill. After kneading for 5 minutes, the mixture was cooled to 55 ° C, and sulfur and a vulcanization accelerator were added thereto, and kneaded at 90 ° C for 3 minutes to prepare a rubber composition. Then, it was vulcanized at 145 ° C, 10 MPa for 38 to 44 minutes using a press (manufactured by Kitagawa Seiki Co., Ltd.) to obtain a vulcanized rubber composition. The ingredients used are disclosed below. Cerium dioxide: trade name "Nipsil AQ" (BET specific surface area = 207 m ² /g, manufactured by Tosoh and cerium oxide). Hydrane coupling agent: bis(3-triethoxydecylpropyl) four Sulfide (made by Evonik Japan Co., Ltd.) Zinc Hua (made by Wako Pure Chemical Industries, Ltd.) Stearic acid (made by Wako Pure Chemical Industries, Ltd.) Sulfur (made by Koijei Chemical Industry Co., Ltd., 250 μm) Vulcanization accelerator (CBS): N-cyclohexyl-2-benzothiazolyl sulfenylamine (manufactured by Wako Pure Chemical Industries, Ltd.) Vulcanization accelerator (DPG): Diphenyl hydrazine (manufactured by Wako Pure Chemical Industries, Ltd.)

(Example 13 and Comparative Example 2) According to the composition of Table 2, the natural rubber solidified body (RSS #1), cerium oxide, decane coupling agent, zinc silicate, stearic acid, and modifier 1 were firstly used as the above Laboplastomill. After kneading at 140 ° C for 5 minutes, the mixture was cooled to 55 ° C, and sulfur and a vulcanization accelerator were added thereto, and kneaded. After reaching 90 ° C, the mixture was further kneaded for 3 minutes to prepare a rubber composition. Then, it was vulcanized at 145 ° C, 10 MPa for 35 to 42 minutes using a press (manufactured by Kitagawa Seiki Co., Ltd.) to obtain a vulcanized rubber composition. The ingredients used (disclosed to Table 1 as the user) are disclosed below. Modifier 1: 1,3-diaminoguanidine hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.)

The heat-producing property and tensile breaking strength of the vulcanized rubber composition were measured and evaluated by the following methods. The results are shown in Tables 1 and 2. (1) Febrile property The dynamic vulcanization measuring device (DMS 6100 manufactured by Seiko Instruments Co., Ltd.) was used to measure the loss tangent (tan δ) at a temperature of 50 ° C, a deformation of 0.5%, and a frequency of 10 Hz. The order of Comparative Example 2 of Example 1 and Table 2 is 100, and the index is expressed separately. The smaller the index is, the lower the tan δ is, indicating that the rubber composition is low in heat. (2) Tensile breaking strength The tensile strength of the vulcanized rubber composition was measured in accordance with JIS K6251:2010, and the tensile breaking strength was measured. The comparison of Comparative Example 1 of Table 1 and Comparative Example 2 of Table 2 was 100, respectively. index. The larger the index, the greater the tensile strength at break.

【Table 1】 In Table 1, each component of the blending formulation represents parts by mass.

It is confirmed from Table 1 that at least the rubber composition of the example is a rubber composition obtained by mixing a diene rubber which has not been modified with a bisalkylenediamine sulfonium salt, and has excellent low heat build-up and tensile fracture. Strong intensity.

【Table 2】 In Table 2, each component of the blending formulation represents parts by mass.

It is also confirmed from Table 2 that the rubber composition of the example is superior to the rubber composition which is mixed without adding a bisalkylenediamine fluorene, and has a low heat build-up property and a large tensile strength at break.

This application is based on a Japanese patent application filed on September 12, 2014 to the Japanese Special Office (Japanese Patent Application No. 2014-186073), and a Japanese patent application filed with the Japanese Patent Office on September 12, 2014 (Japan) Japanese Patent Application No. 2014-186075), the disclosure of which is incorporated herein by reference. [Industry Utilization]

The compound, the modified rubber, and the rubber composition of the present invention can be made of materials such as various tire members mainly composed of tires.

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Claims (15)

a compound represented by formula (1) or formula (2); In the formula, X is an acid which forms a salt with a hydrazine moiety, and R ¹ and R ² are each independently selected from an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, and an alkenyl group ( Each of the groups includes at least one selected from the group consisting of one or more substituents containing a sulfur atom, a nitrogen atom or an oxygen atom, and a hydrogen atom; In the formula, R ¹ and R ² are each independently selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, and an alkenyl group (all of which include one or more). At least one of the group consisting of a sulfur atom, a nitrogen atom, or a substituent of an oxygen atom, and a hydrogen atom. The compound of the first aspect of the patent application is obtained by reacting a compound represented by the formula (3) with a compound represented by the formula (4); Wherein the X-form and the hydrazine moiety of the formula (3) form a salt acid; In the formula, R ¹ and R ² are each independently selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, and an alkenyl group (all of which include one or more At least one of the group consisting of a sulfur atom, a nitrogen atom, or a substituent of an oxygen atom, and a hydrogen atom. The compound of claim 1 or 2, wherein R ¹ and R ^{2 of the} formula (1) or (2) are each independently selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an aryl group, and an alkene group. At least one of a group consisting of a group and a hydrogen atom. The compound of claim 1 or 2 has a melting point of 50 to 300 °C. The compound of claim 1 or 2 is represented by any one of formulas (5) to (10) and (12) to (14); 【化6】 【化7】 【化8】 【化9】 【化10】 【化11】 【化12】 【化13】 A modified rubber (A) obtained by modifying at least one rubber selected from the group consisting of natural rubber and synthetic rubber by the compound of the first or second aspect of the patent application. The modified rubber (A) according to claim 6 of the patent application, wherein the at least one rubber selected from the group consisting of natural rubber and synthetic rubber is represented by the formula (1) or (2) The compound is obtained by mixing and modifying at a temperature of 20 to 180 °C. The modified rubber (A) according to the sixth aspect of the invention, wherein the compound represented by the formula (1) or the formula (2) is used in an amount of 0.01 to 10% by mass based on the total amount of the natural rubber and the synthetic rubber. A rubber composition comprising: a modified rubber (A) according to claim 6 of the patent application, a filler containing an inorganic filler (B), and a decane coupling agent (C). The rubber composition of claim 9, wherein the inorganic filler (B) is cerium oxide. The rubber composition of claim 9, wherein the filler material comprises carbon black. A rubber composition comprising the modified rubber (A) according to claim 9 of the patent application, wherein the compound represented by the formula (1) or the formula (2) is selected from the group consisting of natural rubber and synthetic rubber. At least one rubber in the group, the filler containing the inorganic filler (B), and the decane coupling agent (C) are mixed. The rubber composition of claim 12, wherein the temperature at the time of mixing is in the range of 20 to 180 °C. The rubber composition of claim 12, wherein the compound represented by the formula (1) or the formula (2) is used in an amount of 0.01 to 10% by mass based on the total amount of the natural rubber and the synthetic rubber. A tire for use in a tread of a tire component using a rubber composition as in claim 9 of the patent application.