JP2020083856A - Rotaxane compound - Google Patents

Abstract

To provide a rotaxane compound which functions as a vulcanizer.SOLUTION: A rotaxane compound includes one or more cyclic molecules and a shaft molecule penetrating the inner pore part of the cyclic molecule and having a cap structure arranged such that the cyclic molecule is not eliminated therefrom, in which the cyclic molecule and the shaft molecule have one or more groups selected from a set composed of mercapto and sulfide groups.SELECTED DRAWING: None

Description

The present invention relates to a rotaxane compound which functions as a vulcanizing agent, and a rubber composition containing the rotaxane compound.

Traditionally, rubber is crosslinked with sulfur. Generally, rubber products are required to have high durability, but the cross-linking sites that are linked by covalent bonds, such as sulfur, tend to concentrate stress when a force is applied to the material and become the starting point of fracture. Cheap. Further, a rubber material for a tire is required to have low fuel consumption performance, but stress concentration of the material causes deterioration of the fuel consumption performance.

In recent years, research on rotaxane network polymers (RCP) using rotaxane crosslinking as a key has been actively pursued. Rotaxane is a supramolecular compound in which a chain molecule, which is the axial component, and a cyclic molecule, which is the ring component, are linked by a spatial bond without a covalent bond. It has a high degree of freedom and motility without being restricted by, and thus exhibits unique dynamic characteristics and physical properties. RCP is a general term for cross-linked polymers having a rotaxane structure at the cross-linking point, and it has been reported to exhibit high flexibility and elasticity due to the structure of the movable cross-linking point (Non-Patent Documents 1 to 3). ).

Okumura et al., Advanced Materials (2001), Vol. 13, No. 7, pp. 485-487. Ito, Polymer Journal (2007), Vol. 39, No. 6, pp. 489-499 Koyama et al., Polymer Journal (2014), 46, pp. 315-322.

However, most of the RCPs are polyrotaxane cyclic molecules that include a large number of cyclic molecules and are cross-linked with each other, and their versatility and intended use are limited.

If a technology for designing a low-molecular weight functional rotaxane compound close to the basic unit of rotaxane and precisely controlling the properties of a material having a rotaxane structure as a crosslinking point is provided, its utility is extremely high.

An object of the present invention is to provide a rotaxane compound that functions as a vulcanizing agent, and a rubber composition containing the rotaxane compound.

As a result of intensive studies, the present inventors have found that a novel rotaxane compound in which a mercapto or sulfide is introduced into a cyclic molecule and a shaft molecule of a rotaxane compound is useful vulcanization that imparts unique dynamic properties and physical properties to a compounded composition. They have found that they can be used as agents and have completed the present invention.

That is, the present invention relates to [1] one or more cyclic molecules, and an axial molecule penetrating an inner pore portion of the cyclic molecule, the axial molecule having a cap structure arranged so as not to detach the cyclic molecule. A rotaxane compound containing, wherein the cyclic molecule and the axial molecule have one or more groups selected from the group consisting of mercapto and sulfide,
[2] The rotaxane compound according to [1], wherein the cyclic molecule is at least one selected from the group consisting of crown ethers, cyclodextrins, cyclophanes, calixarenes, cucurbiturils, and pillar arenes.
[3] The rotaxane compound according to [1] or [2], wherein one molecule of the axial molecule penetrates through one molecule of the cyclic molecule,
[4] A polymer composition containing a polymer having a carbon-carbon unsaturated bond and the rotaxane compound according to any one of [1] to [3].
[5] The polymer composition according to [4], wherein the polymer is a diene rubber.
[6] A vulcanizing agent containing the rotaxane compound according to any one of [1] to [3].

The rotaxane compound of the present invention has mercapto or sulfide in a cyclic molecule and an axial molecule and reacts with a diene rubber to form a crosslink, so that it does not use a special modified polymer as a rubber component and is vulcanized. Crosslinking is possible without using sulfur as an agent. In addition, in the polymer composition containing the rotaxane compound, the stress at the cross-linking point is relaxed by the sliding of the rotaxane ring, and it is expected that the material strength and the fuel economy are improved.

In the present specification, the term "compound" is not excluded as being in the form of a free form, a salt, a solvate, an ion or the like, unless otherwise specified, and the form is based on common general technical knowledge. Can be interpreted as Examples of the anion constituting the salt include perchlorate ion, trifluoromethanesulfonate ion, hexafluorophosphate ion, trifluoroacetate ion, and tetrafluoroborate ion.

As used herein, the term "rubber" refers to a raw rubber that can be modified to be essentially insoluble (but swellable) in a boiling solvent such as benzene, methyl ethyl ketone, and an ethanol/toluene azeotrope, or already modified. Means elastomeric material that is being modified.

In the present specification, the "rubber compound" means a compound that is a main component that constitutes rubber. Examples of rubber compounds include rubber hydrocarbons such as cis-1,4-polyisoprene.

<Rotaxane compound>
The rotaxane compound according to the present embodiment is a molecule in which a cyclic molecule and an axial molecule are connected by a spatial bond without a covalent bond, as one skilled in the art would normally understand about a rotaxane. The rotaxane compound according to the present embodiment is one or more cyclic molecules, a shaft molecule that penetrates the inner pore portion of the cyclic molecule, and a shaft having a cap structure arranged so that the cyclic molecule is not detached. The molecule is characterized in that the cyclic molecule and the axial molecule have one or more groups selected from the group consisting of mercapto and sulfide. Therefore, the rotaxane compound according to this embodiment can be used as a novel vulcanizing agent. Note that sulfides include polysulfides such as disulfide and tetrasulfide.

The rotaxane compound according to this embodiment may have at least one asymmetric carbon atom. Therefore, the rotaxane compound according to the present embodiment includes not only its racemate but also the optically active form of these compounds. Furthermore, when the rotaxane compound according to this embodiment has two or more asymmetric carbon atoms, stereoisomerism may occur. Therefore, the rotaxane compound according to this embodiment includes stereoisomers of these compounds, a mixture thereof, and an isolated one.

The rotaxane compound according to this embodiment may exist as a tautomer. Therefore, the rotaxane compound according to the present embodiment also includes tautomers of the compound.

Further, the rotaxane compound according to the present embodiment also includes a deuterium converter obtained by converting any one or two or more 1H of the rotaxane compound according to the present embodiment into 2H(D).

(Circular molecule)
The rotaxane compound according to this embodiment contains one or more cyclic molecules as its constituent molecules. From the viewpoint of ease of synthesis, a rotaxane compound in which one molecule of the axial molecule penetrates for 1 to 3 cyclic molecules (that is, a rotaxane compound that includes 1 to 3 cyclic molecules) is preferable. Further, as a basic unit of rotaxane, from the viewpoint of precisely controlling the property of a material having a rotaxane structure as a cross-linking point, a rotaxane compound (that is, [2 ] Rotaxane) is particularly preferred.

Specific examples of the cyclic molecule include crown ether, cyclodextrin, cyclophane, calixarene, cucurbituril, pillararene and the like. Crown ethers are preferred from the viewpoints of easy availability, convenience, and reactivity such that there are many commercially available products, various structural conversions have been reported, and that the number determined in rotaxane synthesis can be included.

The ring size of the cyclic molecule is preferably 21 to 42 members, more preferably 21 to 30 members, and particularly preferably 24 members.

The cyclic molecule may have one or more substituents. Specific examples of the substituent include, for example, alkylthio, mercapto, aminomethyl, amino, hydroxyl, hydroxymethyl, carboxyl, carboxymethyl, halogen, alkoxy, alkoxycarbonylamino (carbamate), carbamoyl, vinyl, allyl, ethynyl, formyl, Examples thereof include acrylate, methacrylate, ether and the like. Specific examples of the ether include, for example, a polyether which may have one or more substituents selected from the group consisting of a phenyl group and an oxo group. The above-mentioned substituent may be directly substituted on the atom constituting the ring of the cyclic molecule, or may be bonded via a spacer extending from the atom constituting the ring. The spacer is, for example, an alkylene chain, —CO—O—, —O—CO—, —O—, —CO—, —CS—, —NH—, NR ¹ — (wherein R ¹ is an alkyl group or the like. Represents a substituent group), an aromatic ring, a heteroaromatic ring, a saturated or partially unsaturated hydrocarbon ring, and a saturated or partially unsaturated heterocycle, and the like. it can.

Preferred examples of the cyclic molecule include, for example, one or more groups selected from the group consisting of mercapto and sulfide, and may have one or more of the above-mentioned substituents, and the ring-forming oxygen. There are 21 to 42 membered crown ethers in which 1 to 3 of the atoms may be replaced by NH or S.

［式中、各Ｒは、同一または異なって、水素原子またはスペーサーを介していてもよいメルカプト、スルフィド、または置換基を表し；ｎは、２〜９の整数（好ましくは、２〜５の整数）を表し；環構成酸素原子のうちの１〜３個は、ＮＨまたはＳに置き換えられていてもよく；隣接する炭素原子に置換する２つのＲが、それらが結合する炭素原子と一緒になって、芳香族環（好ましくは、ベンゼン環）、複素芳香族環、飽和もしくは部分不飽和の炭化水素環、または飽和もしくは部分不飽和のヘテロ環を形成していてもよい。］で表されるクラウンエーテル環状分子である。 One embodiment of the cyclic molecule has the following formula (1):

[In the formula, each R is the same or different and represents a hydrogen atom or a mercapto, a sulfide, or a substituent which may have a spacer interposed therebetween; n is an integer of 2 to 9 (preferably an integer of 2 to 5). And 1 to 3 of the ring-constituting oxygen atoms may be replaced by NH or S; two R's substituting adjacent carbon atoms are taken together with the carbon atom to which they are attached. And may form an aromatic ring (preferably a benzene ring), a heteroaromatic ring, a saturated or partially unsaturated hydrocarbon ring, or a saturated or partially unsaturated heterocycle. ] It is a crown ether cyclic molecule represented by.

Specific examples of the above substituents include, for example, aminomethyl, amino, hydroxyl, hydroxymethyl, carboxyl, carboxymethyl, halogen, alkoxy, alkoxycarbonylamino (carbamate), carbamoyl, vinyl, allyl, ethynyl, formyl, acrylate, And methacrylate, ether and the like. Specific examples of the ether include, for example, a polyether which may have one or more substituents selected from the group consisting of a phenyl group and an oxo group.

The spacer is, for example, an alkylene chain, —CO—O—, —O—CO—, —O—, —CO—, —CS—, —NH—, NR ¹ — (wherein R ¹ is alkyl. Represents a substituent such as a group), an aromatic ring, a heteroaromatic ring, a saturated or partially unsaturated hydrocarbon ring, and a saturated or partially unsaturated heterocycle. be able to.

Specific examples of the crown ether include dibenzo-24-crown-8, 24-crown-8, benzo-24-crown-8 and bis(binaphthyl), each of which may have one or more substituents. )-28-crown-8, bis(biphenyl)-28-crown-8, dicyclohexyl-24-crown-8, and benzo/binaphthyl-24-crown-8. Among them, dibenzo-24-crown-8, 24-crown-8, benzo-24-crown-8, and dicyclohexyl-24-crown-8, which may each have one or more substituents, are preferable. More preferred is dibenzo-24-crown-8, which may each have one or more substituents.

The mercapto or sulfide may be directly substituted on the atom constituting the ring of the cyclic molecule, or may be bonded via the above spacer extending from the atom constituting the ring.

(Axis molecule)
The rotaxane compound according to the present embodiment contains a shaft molecule as its constituent molecule. The axial molecule has a bulky group having an outer diameter larger than the inner diameter of the cyclic molecule, that is, a cap structure. The position of the cap structure is not particularly limited as long as the axial molecule is not detached from the cyclic molecule, and may be present at the end of the axial molecule or in the middle of the axial molecule.

The cap structure is not particularly limited as long as it is a bulky group that can prevent desorption of the chain molecule from the cyclic molecule, and examples thereof include an optionally substituted monocyclic or polycyclic aromatic group. It can be a group, a heteroaromatic ring, a saturated or partially unsaturated hydrocarbon ring, a saturated or partially unsaturated heterocycle, or an acyclic group having these (for example, an alkyl group). For example, the monocyclic group having a substituent can be a monocyclic ring having one or more bulky substituents such as a tert-butyl group. Specific examples of the bulky group include, for example, aryl optionally substituted with one or more alkyl having 1 to 6 carbon atoms (eg, 3,5-di-tert-butylphenyl, 3,5-dimethylphenyl). , 2,6-dimethylphenyl, 3,5-dinitrophenyl, 4-tert-butylphenyl, 2,4,6-trimethylphenyl, tert-butyl, trityl, naphthyl, anthracenyl) and the like.

The chain length of the linker in the axial molecule is not particularly limited as long as the mobility of the rotaxane compound described above is not lost, but for example, its main chain is 1 to 500, preferably 5 to 100, and more preferably 10 It can be composed of ~50 atoms. The linker may have a substituent as long as the mobility of the rotaxane compound described above is not lost. Specific examples of the substituent include, for example, aminomethyl, amino, hydroxyl, hydroxymethyl, carboxyl, carboxymethyl, halogen, alkoxy, alkoxycarbonylamino (carbamate), carbamoyl, vinyl, allyl, ethynyl, formyl, acrylate, and methacrylate. , Ether and the like. Specific examples of the ether include, for example, a polyether which may have one or more substituents selected from the group consisting of a phenyl group and an oxo group.

The linker may be composed of, for example, a polymer such as polyester, polyether, polyacrylate, or polycarbonate, or a polymer based on these.

Linkers, one or more ammonium portion (preferably secondary ammonium (-N ⁺ H ₂ -) part) may have. During the production of the rotaxane compound, the part retains the positional relationship in which the raw material of the chain molecule penetrates the main ring of the cyclic molecule by electrostatic interaction with the oxygen atom of the cyclic molecule. Can contribute to. The rotaxane compound according to this embodiment having one or more secondary ammonium moieties is a counter anion (for example, perchlorate ion, trifluoromethanesulfonate ion, hexafluorophosphate ion, trifluoroacetate ion, and tetrafluoroborohydride ion). Acid ion etc.) may be contained.

The linker has, for example, one or more secondary ammonium moieties, and has an alkylene chain, -CO-O-, -O-CO-, -O-, -CO-, -CS-, -NH-, NR ¹ — (wherein R ¹ represents a substituent such as an alkyl group), an aromatic ring, a heteroaromatic ring, a saturated or partially unsaturated hydrocarbon ring, and a saturated or partially unsaturated heterocycle. Can have a structural unit selected from the group consisting of:

The mercapto or sulfide may be directly substituted on the atom constituting the linker or cap structure, or may be bonded via the above spacer extending from the atom constituting the linker or cap structure.

［式中、環Ａは、環構成酸素原子のうちの１〜３個がＮＨ、またはＳに置き換えられていてもよいクラウンエーテル環状分子を表し；各Ｒは、同一または異なって、水素原子またはスペーサーを介していてもよいメルカプト、スルフィド、または置換基を表し；隣接する炭素原子に置換する２つのＲが、それらが結合する炭素原子と一緒になって、芳香族環（好ましくは、ベンゼン環）、複素芳香族環、飽和もしくは部分不飽和の炭化水素環、または飽和もしくは部分不飽和のヘテロ環を形成していてもよく；ｎは、２〜９の整数（好ましくは、２〜５の整数）を表し；ｍは１、または２以上の繰り返し数を表し；軸分子Ｂは、ｍ個の２級アンモニウム（−Ｎ⁺Ｈ₂−）部を有し；Ｂ¹およびＢ²は、同一または異なって、キャップ構造を表し；Ｘ^-は、２級アンモニウム塩のカウンターアニオンを表す。］で表される化合物である。 A preferred aspect of the rotaxane compound according to the present embodiment is the following formula (2):

[Wherein, ring A represents a crown ether cyclic molecule in which 1 to 3 of ring-constituting oxygen atoms may be replaced by NH or S; each R is the same or different, and is a hydrogen atom or Represents a mercapto, a sulfide, or a substituent which may be separated by a spacer; two Rs substituting adjacent carbon atoms, together with the carbon atom to which they are bound, form an aromatic ring (preferably a benzene ring). ), a heteroaromatic ring, a saturated or partially unsaturated hydrocarbon ring, or a saturated or partially unsaturated heterocycle; n is an integer of 2 to 9 (preferably 2 to 5). An integer); m is 1 or a repeating number of 2 or more; the axis molecule B has m secondary ammonium (-N ⁺ H ₂ -) moieties; B ¹ and B ² are the same. Or, differently, represents a cap structure; X ⁻ represents a counter anion of the secondary ammonium salt. ] It is a compound represented by.

X ^- include specific examples of the counter anion represented by, for example, perchlorate ion, trifluoromethanesulfonate ion, hexafluorophosphate ion, trifluoroacetate ion, and tetrafluoroborate, and the like.

Specific examples of the above substituents include, for example, aminomethyl, amino, hydroxyl, hydroxymethyl, carboxyl, carboxymethyl, halogen, alkoxy, alkoxycarbonylamino (carbamate), carbamoyl, vinyl, allyl, ethynyl, formyl, acrylate, And methacrylate, ether and the like. Specific examples of the ether include, for example, a polyether which may have one or more substituents selected from the group consisting of a phenyl group and an oxo group.

The spacer is, for example, an alkylene chain, —CO—O—, —O—CO—, —O—, —CO—, —CS—, —NH—, NR ¹ — (wherein R ¹ is alkyl. Represents a substituent such as a group), an aromatic ring, a heteroaromatic ring, a saturated or partially unsaturated hydrocarbon ring, and a saturated or partially unsaturated heterocycle. be able to.

Further, a compound obtained by converting one or more secondary ammonium (—N ⁺ H ₂ —) moieties of the compound represented by the formula (2) into tertiary ammonium, amide, urea, carbamate and the like is also mentioned as a preferred embodiment.

<Method for producing rotaxane compound>
The rotaxane compound according to the present embodiment, a known method such as Threading-Capping method, a method described in the literature (for example, Oleoscience Vol. 5, No. 5, 2005, p. 209) or a method according thereto, It can be manufactured.

The mercapto group and the sulfide group can be introduced, for example, starting from an alkenyl group introduced into a cyclic molecule or a shaft molecule. Specifically, for example, a mercapto group and a sulfide group can be introduced into the cyclic molecule or the axis molecule by adding an alkylthiol or an alkyldithiol to the alkenyl group introduced into the cyclic molecule or the axis molecule.

The rotaxane compound and its intermediate according to the present embodiment are subjected to a purification method commonly used in synthetic organic chemistry, for example, neutralization, filtration, extraction, washing, drying, concentration, recrystallization, various chromatography, etc. It can be purified separately. In addition, each intermediate can be subjected to the next reaction without being particularly purified.

The optically active substance of the rotaxane compound according to the present embodiment can be produced by using an optically active starting material or intermediate, or by optically resolving the racemate of the final product. Examples of the optical resolution method include a physical separation method using an optically active column and a chemical separation method such as a fractional crystallization method. The diastereomer of the rotaxane compound according to this embodiment is produced by, for example, a fractional crystallization method.

<Polymer composition>
The rotaxane compound according to this embodiment can be used as a vulcanizing agent to produce a polymer composition. The polymer composition containing the rotaxane compound can be expected to have improved stretchability, stress relaxation property, wear resistance and the like.

Applications of the polymer composition include, for example, tire materials, optical materials, medical materials, biomaterials, contact lenses, coating agents, and adhesives; and environment-related materials, daily necessities, civil engineering building materials, battery-related materials. , Foods, health goods, sports goods and their materials, clothing/fashion materials, textiles, toys/entertainment materials, art-related materials, automobile-related materials, and the like, but are not limited thereto.

The polymer contained in the polymer composition according to the present embodiment is not particularly limited as long as it is a polymer that reacts with mercapto and/or sulfide to form a crosslinked structure, and examples thereof include acrylonitrile-butadiene copolymer and polyisoprene. , Styrene-butadiene copolymer, polybutadiene, polychloroprene, ethylene-propylene-diene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer such as carbon-carbon unsaturated bond The polymer which has is mentioned.

Specific examples of the case where the polymer is a rubber compound include, for example, a diene compound that is a compound having a carbon-carbon double bond (C=C); an EPDM (ethylene-propylene-diene copolymer rubber) compound; a polynorbornene. And a NBR (nitrile rubber) compound which is a compound having a nitrile group and a carbon-carbon double bond in the molecule.

Examples of the diene rubber include isoprene rubber including natural rubber (NR) and polyisoprene rubber (IR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), styrene-isoprene-butadiene copolymer rubber. (SIBR), chloroprene rubber (CR) and the like.

When NR is contained, the content in the rubber component is, for example, 1 to 100% by mass, 5 to 95% by mass, 10 to 90% by mass, 1 to 20% by mass, 5 to 30% by mass, and 10 to 40% by mass. 20-50 mass %, 30-60 mass %, 40-70 mass %, 50-80 mass %, 60-90 mass %, 70-100 mass %, or 80-100 mass %.

When the BR is contained, the content in the rubber component is, for example, 1 to 100% by mass, 5 to 95% by mass, 10 to 90% by mass, 1 to 20% by mass, 5 to 30% by mass, and 10 to 40% by mass. 20-50 mass %, 30-60 mass %, 40-70 mass %, 50-80 mass %, 60-90 mass %, 70-100 mass %, or 80-100 mass %.

When SBR is contained, the content in the rubber component is, for example, 1 to 100% by mass, 5 to 95% by mass, 10 to 90% by mass, 1 to 20% by mass, 5 to 30% by mass, and 10 to 40% by mass. 20-50 mass %, 30-60 mass %, 40-70 mass %, 50-80 mass %, 60-90 mass %, 70-100 mass %, or 80-100 mass %.

Applications of rubber include tires, hoses, belts, packings, electric wire coatings, anti-vibration rubbers, building rubbers, rollers, footwear, seal parts, medical materials, automotive parts, daily necessities, sports equipment, batteries, etc. ..

Specific examples when the polymer is a water-soluble polymer include, for example, starch, gelatin, carboxymethylcellulose, methylcellulose, polyamine, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyethylene oxide, polyvinylpyrrolidone, polyvinylamide, and polypeptides. Can be mentioned.

Examples of the use of the water-soluble polymer include pharmaceuticals, medical materials, cosmetics, toiletries, foods, paints, adhesives, inks, civil engineering, water treatment such as wastewater treatment, electronics, batteries and the like.

The polymer composition using the rotaxane compound according to the present embodiment as a vulcanizing agent is excellent in low fuel consumption performance, wear resistance performance, and breaking strength, and thus is suitably used as a tire member.

The usage amount of the rotaxane compound according to the present embodiment can be appropriately changed depending on the molecular weight of the rotaxane compound, but with respect to 100 parts by mass of the polymer having an unsaturated bond, for example, 1 to 200 parts by mass and 2 to 160 parts by mass. Parts, 5 to 140 parts by mass, 10 to 120 parts by mass, and 20 to 100 parts by mass.

Silica is preferably used as the filler contained in the polymer composition according to the present embodiment. The silica is not particularly limited, and for example, silica prepared by a dry method (anhydrous silica), silica prepared by a wet method (hydrous silica), and the like can be used. Of these, hydrous silica prepared by the wet method is preferable because it has many silanol groups. The silica may be used alone or in combination of two or more kinds.

From the viewpoint of elongation at break, the nitrogen adsorption specific surface area (N ₂ SA) of silica is preferably 80 m ² /g or more, more preferably 100 m ² /g or more, still more preferably 110 m ² /g or more. The N ₂ SA of the silica, from the viewpoint of fuel efficiency and workability, preferably 250 meters ² / g or less, more preferably 235m ² / g, more preferably not more than 220 m ² / g. The N ₂ SA of silica in the present specification is a value measured by the BET method according to ASTM D3037-93.

The content with respect to 100 parts by mass of the rubber component when containing silica is not particularly limited and can be appropriately selected according to the purpose. For example, 1 to 150 parts by mass, 10 to 140 parts by mass, and 20 to 130 parts by mass. , 30 to 120 parts by mass, 40 to 110 parts by mass, and 60 to 100 parts by mass. From the viewpoint of low fuel consumption performance, the content of silica is preferably 60 parts by mass or more, more preferably 65 parts by mass or more, and even more preferably 70 parts by mass or more with respect to 100 parts by mass of the rubber component. Further, from the viewpoint of the dispersibility of silica and the processability, the amount is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, and further preferably 110 parts by mass or less.

When silica is contained, it is preferable to use a silane coupling agent together. As the silane coupling agent, any silane coupling agent conventionally used in combination with silica in the rubber industry can be used. For example, Si75, Si266 (bis(3-triethoxysilylpropyl) manufactured by Evonik Degussa Co., Ltd. can be used. ) Disulfide), Si69 (bis(3-triethoxysilylpropyl) tetrasulfide) and other silane coupling agents having a sulfide group; 3-mercaptopropyltrimethoxysilane, Momentive NXT-Z100, NXT-Z45, NXT. Silane coupling agent having a mercapto group such as; silane coupling agent having a vinyl group such as vinyltriethoxysilane and vinyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltri A silane coupling agent having an amino group such as ethoxysilane and 3-(2-aminoethyl)aminopropyltrimethoxysilane; γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glyce Glycidoxy-based silane coupling agents such as cidoxypropylmethyldiethoxysilane and γ-glycidoxypropylmethyldimethoxysilane; nitro-based silane coupling agents such as 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane Agents; chloro-type silane coupling agents such as 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane; and the like. These silane coupling agents may be used alone or in combination of two or more. Of these, sulfide type and mercapto type are preferable because they have a strong bonding force with silica and are excellent in low heat buildup.

From the viewpoint of silica dispersibility, the content of the silane coupling agent based on 100 parts by mass of silica is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more. From the viewpoint of cost, it is preferably 25 parts by mass or less, more preferably 20 parts by mass or less.

In addition to silica, other fillers may be used. The filler is not particularly limited, and examples thereof include carbon black, aluminum hydroxide, alumina (aluminum oxide), calcium carbonate, talc, clay and the like, and carbon black is preferably used from the viewpoint of reinforcement. Be done. These fillers may be used alone or in combination of two or more.

As the carbon black, those generally used for rubber can be appropriately used. Specifically, N110, N115, N120, N125, N134, N135, N219, N220, N231, N234, N293, N299, N326, N330, N339, N343, N347, N351, N356, N358, N375, N539, N550,. N582, N630, N642, N650, N660, N683, N754, N762, N765, N772, N774, N787, N907, N908, N990, N991, etc. can be preferably used, and in-house synthesized products are also suitable. Can be used for.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 60 m ² /g or more, more preferably 70 m ² /g or more, still more preferably 80 m ² /g or more. The upper limit of N ₂ SA of carbon black is not particularly limited, but from the viewpoint of workability, it is preferably 180 m ² /g or less, more preferably 160 m ² /g or less, still more preferably 150 m ² /g or less. The N ₂ SA of carbon black in the present specification is measured according to JIS K 6217-2 “Basic characteristics of carbon black for rubber-Part 2: Determination of specific surface area-Nitrogen adsorption method-single point method”. It is a value.

The content with respect to 100 parts by mass of the rubber component when containing carbon black is not particularly limited and can be appropriately selected according to the purpose. For example, 1 to 150 parts by mass, 2 to 130 parts by mass, and 3 to 100 parts by mass. Parts, 3 to 50 parts by mass, 5 to 40 parts by mass, and 5 to 30 parts by mass. From the viewpoint of abrasion resistance, the content of carbon black is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more with respect to 100 parts by mass of the rubber component. Further, the upper limit of the content of carbon black is not particularly limited, but from the viewpoint of low fuel consumption performance and workability, it is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, and further preferably 40 parts by mass or less.

The content of the entire filler with respect to 100 parts by mass of the rubber component is not particularly limited and can be appropriately selected depending on the purpose. For example, 1 to 200 parts by mass, 10 to 150 parts by mass, 30 to 130 parts by mass, 40 to 40 parts by mass. It may be in the range of 110 parts by mass and 50 to 105 parts by mass. From the viewpoint of wear resistance, the content of the entire filler with respect to 100 parts by mass of the rubber component is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, further preferably 60 parts by mass or more, and particularly preferably 80 parts by mass or more. .. Further, from the viewpoint of the dispersibility of silica and the processability, the amount is preferably 150 parts by mass or less, more preferably 140 parts by mass or less, and further preferably 130 parts by mass or less.

From the viewpoint of low fuel consumption performance, the content of silica in the filler is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more.

When the polymer composition according to the present embodiment is a rubber composition for tires, in addition to the above-mentioned polymers and fillers, compounding agents and additives conventionally used in the tire industry, for example, waxes, oils, and antioxidants. , Stearic acid, zinc oxide, a vulcanizing agent, a vulcanization accelerator and the like can be appropriately contained as necessary.

The content of 100 parts by mass of the rubber component when the wax is contained is not particularly limited, and can be, for example, in the range of 0.5 to 10 parts by mass, 0.5 to 5 parts by mass, and 1 to 3 parts by mass. ..

The content of 100 parts by mass of the rubber component when the oil is contained is not particularly limited, and may be, for example, 5 to 100 parts by mass, 10 to 70 parts by mass, or 10 to 50 parts by mass.

The antioxidant is not particularly limited, and those used in the rubber field can be used, and examples thereof include quinoline-based, quinone-based, phenol-based, and phenylenediamine-based antioxidants.

The content of the anti-aging agent with respect to 100 parts by mass of the rubber component is not particularly limited, and is, for example, 0.5 to 10 parts by mass, 0.5 to 5 parts by mass, or 1 to 4 parts by mass. You can

The content of 100 parts by mass of the rubber component when stearic acid is contained is not particularly limited, and may be, for example, 0.2 to 10 parts by mass, 0.5 to 5 parts by mass, or 1 to 3 parts by mass. it can.

The content of 100 parts by mass of the rubber component when zinc oxide is contained is not particularly limited, and may be, for example, 0.5 to 10 parts by mass, 0.5 to 5 parts by mass, or 1 to 3 parts by mass. it can.

The rubber composition according to the present embodiment may contain a vulcanizing agent other than the rotaxane compound according to the present embodiment. As the vulcanizing agent, powdered sulfur, oil-treated sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur and the like can be used.

The content of 100 parts by mass of the rubber component when sulfur is contained as a vulcanizing agent is preferably less than 0.2 parts by mass, more preferably less than 0.1 parts by mass, further preferably less than 0.05 parts by mass, and 0 Part by weight (ie not containing sulfur) is particularly preferred.

Examples of the vulcanization accelerator include sulfenamide-based, thiazole-based, thiuram-based, thiourea-based, guanidine-based, dithiocarbamic acid-based, aldehyde-amine-based or aldehyde-ammonia-based, imidazoline-based, and xanthate-based vulcanization accelerators. Etc. These vulcanization accelerators may be used alone or in combination of two or more kinds. Of these, sulfenamide-based vulcanization accelerators, thiazole-based vulcanization accelerators, and guanidine-based vulcanization accelerators are preferable, and sulfenamide-based vulcanization accelerators are more preferable. Further, a combination of a sulfenamide-based vulcanization accelerator and another vulcanization accelerator (preferably a thiazole-based vulcanization accelerator and/or a guanidine-based vulcanization accelerator) can be mentioned as a preferred embodiment.

Examples of the sulfenamide vulcanization accelerator include N-tert-butyl-2-benzothiazolyl sulfenamide (TBBS), N-cyclohexyl-2-benzothiazolyl sulfenamide (CBS), and N,N. -Dicyclohexyl-2-benzothiazolylsulfenamide (DCBS) and the like. Among them, N-tert-butyl-2-benzothiazolylsulfenamide (TBBS) and N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) are preferable.

Examples of the thiazole vulcanization accelerator include 2-mercaptobenzothiazole, a cyclohexylamine salt of 2-mercaptobenzothiazole, and di-2-benzothiazolyl disulfide. Of these, 2-mercaptobenzothiazole is preferable.

As the guanidine vulcanization accelerator, for example, 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, di-o-tolylguanidine salt of dicatecholborate, 1, Examples thereof include 3-di-o-cumenylguanidine, 1,3-di-o-biphenylguanidine, and 1,3-di-o-cumenyl-2-propionylguanidine. Of these, 1,3-diphenylguanidine is preferable.

The content with respect to 100 parts by mass of the rubber component when the vulcanization accelerator is contained is not particularly limited, and is, for example, 0.1 to 5.0 parts by mass, 0.5 to 4.5 parts by mass, 0.5 to 4 parts by mass. It can be in the range of 0.0 parts by mass.

The polymer composition according to this embodiment can be produced by a known method. For example, when the polymer composition is a rubber composition, it can be produced by a method in which the above components are kneaded using a rubber kneading device such as an open roll, a Banbury mixer, a closed kneader, and then vulcanized. ..

The present invention will be described based on examples, but the present invention is not limited to the examples.

Hereinafter, various chemicals used in Examples and Comparative Examples will be summarized.
SBR: SBR1500 manufactured by JSR Corporation
BR: BR150B manufactured by Ube Industries, Ltd.
Silica: ZEOSIL 1165MP (N ₂ SA: 160 m ² /g) manufactured by Rhodia
Silane coupling agent: Si69 (bis(3-triethoxysilylpropyl)tetrasulfide) manufactured by Evonik Degussa
Carbon black: Diablack N339 (N ₂ SA: 96 m ² /g) manufactured by Mitsubishi Chemical Corporation
Stearic acid: stearic acid "Tsubaki" manufactured by NOF CORPORATION
Wax: Sunnock N manufactured by Ouchi Shinko Chemical Industry Co., Ltd.
Anti-aging agent: Antigen 3C (N-isopropyl-N'-phenyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd.
Zinc oxide: Zinc Hua No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Powder sulfur vulcanization accelerator manufactured by Tsurumi Chemical Industry Co., Ltd. 1: Nocceller CZ (N-cyclohexyl-manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) 2-benzothiazolylsulfenamide)
Vulcanization accelerator 2: Noxcellar D (N,N'-diphenylguanidine) manufactured by Ouchi Shinko Chemical Industry Co., Ltd.

(Synthesis of rotaxane compound)
The rotaxane compound (1-3) was synthesized by the method and conditions shown by the following formula.

Synthesis of Rotaxane Compound (1-1) Axial molecular component (1-a) (1.2 g) was added to a solution of cyclic molecular component (1-r) (1.3 g) in dichloromethane (5.4 mL) and stirred for 2 hours. . Subsequently, 3,5-dimethylphenyl isocyanate (0.49 g) and dibutyltin dilaurate (0.30 g) were added, and the mixture was stirred at room temperature for 3 days. The reaction solution was filtered, the solvent of the filtrate was evaporated, and the residue was purified using preparative GPC (eluent: chloroform) to obtain a rotaxane compound (1-1) (1.3 g).
ESI-MS: m/z calcd for C ₆₉ H ₉₇ N ₂ O ₁₄ Na [M-PF ₆ ] ⁺ : 1097.7, found: 1097.1.

Synthesis of Rotaxane Compound (1-3) Acetic anhydride (0.14 mL) and triethylamine (0.27 mL) were added to a solution of compound (1-1) (0.34 g) in tetrahydrofuran (2.7 mL), and the mixture was heated at 50°C. Stir for 12 hours. The solvent was distilled off to obtain a rotaxane compound (1-2) (0.24 g). Toluene (2.6 mL), 1,10-decanedithiol (45 mg) and azobisisobutyronitrile (56 mg) were added to a part (50 mg) of the obtained rotaxane compound (1-2), and the mixture was heated at 60°C. Stir for 18 hours. After the reaction solution was filtered, the solvent of the filtrate was distilled off and the residue was purified using preparative GPC (eluent: chloroform) to obtain a rotaxane compound (1-3) (40 mg).
¹ H-NMR (500Hz, CDCl ₃ , 298K): δ (ppm) 8.36 (d, 1H, J=10Hz), 7.19-6.49 (m, 12H), 4.48-0.91(m, 128H);
¹³ C-NMR (125Hz, CDCl ₃ , 298K): δ (ppm) 170.9, 170.5, 155.3, 155.2, 154.1, 148.4, 148.0, 140.0, 138.0, 133.8, 131.9, 131.5, 130.9, 128.3, 126.4, 123.3, 120.7 , 120.0, 115.9, 111.7, 111.5, 72.8, 72.1, 72.0, 69.9, 69.7, 68.1, 68.0, 67.9, 64.8, 51.3, 47.8, 47.4, 46.0, 39.1, 34.0, 33.4, 32.4, 32.2, 32.1, 32.0, 30.1 , 29.7, 29.6, 29.5, 29.4, 29.2, 29.1, 29.0, 28.9, 28.4, 28.3, 27.6, 27.1, 26.9, 26.8, 25.8, 25.7, 25.6, 25.5, 24.7, 21.9, 21.5, 21.3, 16.4, 16.3;
ESI-MS: m/z calcd for C ₈₉ H ₁₄₂ N ₂ O ₁₄ S ₂ [M+H] ⁺ : 1551.9, found: 1552.3.

(Examples and Comparative Examples)
According to the formulation shown in Table 1, a rotaxane compound, sulfur and chemicals other than sulfur and a vulcanization accelerator were kneaded at a discharge temperature of 150° C. for 5 minutes using a 1.7 L Banbury mixer manufactured by Kobe Steel Ltd., and kneaded. I got a thing. Next, a rotaxane compound, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and the mixture was kneaded for 5 minutes at 100° C. using an open roll to obtain an unvulcanized rubber composition. Further, the obtained unvulcanized rubber composition was press-vulcanized at 170° C. for 20 minutes to obtain a vulcanized rubber composition for testing (vulcanized rubber sheet).

<Low fuel consumption performance>
Using a viscoelasticity spectrometer VES (manufactured by Iwamoto Manufacturing Co., Ltd.), the loss tangent (tan δ) of each vulcanized rubber sheet for test under conditions of temperature of 50° C., initial strain of 10%, dynamic strain of 2%, and frequency of 10 Hz. Was measured, and the value of the reciprocal of tan δ was indexed with Comparative Example 1 being 100. The larger the value is, the smaller the rolling resistance is (the less heat is generated, the lower the energy loss is), and the better the fuel economy is.
(Low fuel consumption performance index)=(tan δ of Comparative Example 1)/(tan δ of each blend)×100

<Abrasion resistance>
Using a LAT tester (Laboratory Abrasion and Skid Tester), the volume loss of each vulcanized rubber composition for a test was measured under the conditions of a load of 50 N, a speed of 20 km/h and a slip angle of 5°. Regarding the value of the reciprocal number, the value of Comparative Example 1 was set to 100 and displayed as an index. The larger the index, the better the abrasion resistance performance.
(Abrasion resistance index)=(Volume loss amount of Comparative Example 1)/(Volume loss amount of each composition)×100

<Fracture strength>
According to JIS K 6251:2010 “Vulcanized Rubber and Thermoplastic Rubber-Determination of Tensile Properties”, using a No. 3 dumbbell-shaped test piece composed of a vulcanized rubber sheet for each test, at 23° C. A tensile test was performed to measure the breaking strength TB (MPa) and the elongation at break EB (%). The result was shown as an index with Comparative Example 1 as 100. The larger the value, the better the breaking strength.
(Breaking strength index)=(TB of each composition)/(TB of Comparative Example 1)×100
(Elongation at break)=(EB of each composition)/(EB of Comparative Example 1)×100

From the results in Table 1, it can be seen that the rubber composition containing the predetermined rotaxane compound of the present invention has improved fuel economy performance, wear resistance performance, and breaking strength.

The rotaxane compound of the present invention can be used as a vulcanizing agent that imparts unique dynamic properties and physical properties to a compounded composition.

Claims (6)

A rotaxane compound comprising one or more cyclic molecules, and an axial molecule penetrating an inner pore portion of the cyclic molecule, the axial molecule having a cap structure arranged so as not to detach the cyclic molecule. ,
A rotaxane compound in which the cyclic molecule and the axis molecule have one or more groups selected from the group consisting of mercapto and sulfide. The rotaxane compound according to claim 1, wherein the cyclic molecule is at least one selected from the group consisting of crown ethers, cyclodextrins, cyclophanes, calixarenes, cucurbiturils, and pillar arenes. The rotaxane compound according to claim 1, wherein one molecule of the axial molecule penetrates through one molecule of the cyclic molecule. A polymer composition comprising a polymer having a carbon-carbon unsaturated bond and the rotaxane compound according to any one of claims 1 to 3. The polymer composition according to claim 4, wherein the polymer is a diene rubber. A vulcanizing agent containing the rotaxane compound according to claim 1.