Rotaxane compound
View Patent ↗A rotaxane compound comprising one or more cyclic molecules and an axial molecule penetrating through inner holes of the cyclic molecules and having cap structures disposed lest the cyclic molecules should be detached, where one of the cyclic molecule and the axial molecule has one of a functional group being capable of reacting with silica and a functional group being capable of reacting with a carbon-carbon unsaturated bond, and the other of the cyclic molecule and the axial molecule has the other of the functional group being capable of reacting with silica and the functional group being capable of reacting with a carbon-carbon unsaturated bond.
1. A rotaxane compound comprising:
one or more cyclic molecules and an axial molecule penetrating through inner holes of the cyclic molecules and having cap structures disposed lest the cyclic molecules should be detached,
wherein:
one of the cyclic molecule or the axial molecule has one of a functional group being capable of reacting with silica or a functional group being capable of reacting with a carbon-carbon unsaturated bond, and the other one of the cyclic molecule or the axial molecule has the other one of the functional group being capable of reacting with silica or the functional group being capable of reacting with a carbon-carbon unsaturated bond,
the cyclic molecule is a crown ether cyclic molecule represented by the following formula (1a), (1b), or (1c):
wherein:
W 4 is a single bond, or a spacer composed of 1 to 100 atoms and having one or more constituent units selected from the group consisting of linear or branched alkylene chain, —CO—O—, —O—CO—, —O—, —CO—, —S—, —CS—, —NH— and —NR 1 —, where R 1 is an alkyl group having 1 to 6 carbon atoms, a benzene ring, a heteroaromatic ring, a saturated or partially unsaturated hydrocarbon ring, or a saturated or partially unsaturated hetero ring;
R 3 is a functional group capable of reacting with silica or a functional group being capable of reacting with a carbon-carbon unsaturated bond;
the crown ether represented by formula (1a), (1b), or (1c) may be substituted with the same or different 1 to 4 groups independently selected from the group consisting of halogen, alkyl, and alkoxy; and 1 to 3 of oxygen atoms constituting the ring may be replaced by NH or S, and if there are plural cyclic molecules in the rotaxane compound, the cyclic molecules may be the same or different;
the axial molecule is an axial molecule represented by the following formula (3):
wherein:
B 1 and B 2 are independently a cap structure having an outer diameter larger than an inner diameter of the cyclic molecule, wherein at least one of B1 and B2 is selected from the group consisting of phenyl, tert-butyl, diphenylmethyl, trityl, naphthyl, and anthracenyl;
W 1 and W 2 are independently a single bond, or a spacer being composed of 1 to 100 atoms and having one or more constituent unit selected from the group consisting of linear or branched alkylene chain, —CO—O—, —O—CO—, —O—, —CO—, —S—, —CS—, —NH—, and —NR 1 — where R 1 is an alkyl group having 1 to 6 carbon atoms, a benzene ring, a heteroaromatic ring, a saturated or partially unsaturated hydrocarbon ring, or a saturated or partially unsaturated hetero ring;
at least either one of B 1 or B 2 is substituted with —W 3 —R 2 , where:
W 3 is a single bond, or a spacer being composed of 1 to 100 atoms and having one or more constituent unit selected from the group consisting of linear or branched alkylene chain, —CO—O—, —O—CO—, —O—, —CO—, —S—, —CS—, —NH—, and —NR 1 —, where R 1 is an alkyl group having 1 to 6 carbon atoms, a benzene ring, a heteroaromatic ring, a saturated or partially unsaturated hydrocarbon ring, or a saturated or partially unsaturated hetero ring;
R 2 is the functional group being capable of reacting with silica or the functional group being capable of reacting with a carbon-carbon unsaturated bond;
B 1 and B 2 may be substituted with the same or different 1 to 4 groups independently selected from the group consisting of halogen, alkyl, and alkoxy;
hydrogen atoms in the secondary ammonium —N + H 2 — moiety of formula (3) may be substituted with alkyl, alkylcarbonyl, alkylaminocarbonyl, alkoxycarbonyl, optionally-substituted phenylcarbonyl, optionally-substituted phenylaminocabonyl, or optionally-substituted phenoxycarbonyl; and
when a plurality of R 1 , R 2 and W 3 exists, those may be the same or different,
the functional group being capable of reacting with a carbon-carbon unsaturated bond is at least one selected from the group consisting of nitrile oxide, azide, nitron, nitrileimine, sydnone, methylolphenol, mercapto, sulfide, vinyl, vinylene, ethynyl, ethynylene, cyano, isocyanate, isocyanurate, epoxy, glycidyloxy, acryloyl, methacryloyl and ureido, and
the functional group being capable of reacting with silica is at least one selected from the group consisting of alkoxysilyl, acetoxysilyl and chlorosilyl.
2. The rotaxane compound of claim 1 , wherein one of the axial molecules penetrates one of the cyclic molecules.
3. A polymer composition comprising a polymer having a carbon-carbon unsaturated bond and the rotaxane compound of claim 1 .
4. The polymer composition of claim 3 , wherein the polymer is a diene rubber.
5. A rubber composition comprising a diene rubber, silica and the rotaxane compound of claim 1 .
6. The rotaxane compound of claim 1 , wherein the alkoxysilyl is trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethylmethoxysilyl or dimethylethoxysilyl.