Polyrotaxane, thermally curable composition including said polyrotaxane, thermally cured crosslinked object, production method for polyrotaxane, and production method for thermally cured crosslinked object
The present invention provides a polyrotaxane for obtaining a material combining a higher degree of elongation with a higher breaking strength and/or a polyrotaxane having properties not possessed by conventional polyrotaxanes, such as compatibility with compounds to be used in a material, solubility in solvents, and functionality. The polyrotaxanes of the present invention each comprise: a pseudo-polyrotaxane comprising cyclic molecules and a linear molecule which passes through the cavities of the cyclic molecules to form a clathrate; and blocking groups disposed at both ends of the pseudo-polyrotaxane so that the cyclic molecules are not released. The cyclic molecules each include a hydroxyl-inactivation group and a hydroxyl group bonded by a spacer group. The polyrotaxanes have a hydroxyl value of 10-65 mg-KOH/g.
1. A thermosetting composition comprising:
A) a polyrotaxane comprising capping groups each locating at each end of a pseudopolyrotaxane, which has a linear molecule and a cyclic molecule(s) in which the linear molecule is included in a cavity (cavities) of the cyclic molecule(s) in a skewered manner, in order to prevent the dissociation of the cyclic molecule(s),
wherein the cyclic molecule comprises a group having an ability to inactivate a hydroxyl group and a hydroxyl group bonded through a spacer group, and the polyrotaxane has a hydroxyl value of 10 to 65 mgKOH/g; and
B) a material which is capable of reacting with the hydroxyl group of the A) polyrotaxane to cure,
wherein the material comprises one selected from the group consisting of polycarbonates with terminal isocyanate modification, polypropylene glycol with terminal isocyanate modification, a polyacryl ester having an isocyanate side chain, polycarbonates with terminal isothiocyanate modification, a polyacrylic acid ester having an isothiocyanate group in a side chain, an acid-anhydride-modified polypropylene, polyethylene glycol with terminal epoxy-modification, and acryl polymers modified with carboxylic acid group.
2. The composition according to claim 1 , wherein an amount of the A) polyrotaxane is 2 to 35% by weight based on 100% by weight of the total nonvolatile components of the composition.
3. The composition according to claim 1 , wherein the spacer group has a group derived from polycaprolactone.
4. The composition according to claim 1 , wherein the spacer group further has a group derived from hydroxypropyl.
5. The composition according to claim 1 , wherein the group having an ability to inactivate a hydroxyl group is selected from the group consisting of alkyl ester groups, alkyl carbamoyl groups, and alkyl ether groups, wherein the alkyl of each of the alkyl carbamoyl groups independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms.
6. The composition according to claim 1 , wherein the B) material further comprises a b) second compound having a number average molecular weight of 350 or more and having at least two groups selected from a hydroxyl group, an amino group, and a thiol group.
7. The composition according to claim 6 , further comprises C) a crosslinking agent.
8. The composition according to claim 7 , wherein the 2) second compound is a polyol having two or more hydroxyl groups, and the C) crosslinking agent has two or more isocyanate groups.
9. A thermoset crosslinked body formed from the composition according to claim 1 .
10. A method for producing a thermoset crosslinked body, comprising the steps of:
a) preparing a polyrotaxane, in which capping groups each locates at each end of a pseudopolyrotaxane, which has a linear molecule and a cyclic molecule(s) having a hydroxyl group(s) in which the linear molecule is included in a cavity (cavities) of the cyclic molecule(s) in a skewered manner, in order to prevent the dissociation of the cyclic molecule(s),
b) mixing and reacting a compound, which serves as a source of a group having an ability to inactivate a hydroxyl group that is converted to a group having an ability to inactivate a hydroxyl group, to and with the polyrotaxane to inactivate a part of the hydroxyl group(s);
to obtain a polyrotaxane having a hydroxyl value of 10 to 65 mgKOH/g, and
d) mixing the obtained polyrotaxane with a material which reacts with a hydroxyl group(s) of the polyrotaxane, to cure, and reacting the resultant by applying heat;
to obtain the thermoset crosslinked body,
wherein the material comprises one selected from the group consisting of polycarbonates with terminal isocyanate modification, polypropylene glycol with terminal isocyanate modification, a polyacryl ester having an isocyanate side chain, polycarbonates with terminal isothiocyanate modification, a polyacrylic acid ester having an isothiocyanate group in a side chain, an acid-anhydride-modified polypropylene, polyethylene glycol with terminal epoxy-modification, and acryl polymers modified with carboxylic acid group.
11. The method according to claim 10 ,
wherein in the step a), the hydroxyl group is directly bound to a cyclic molecule;
the method comprising, after the step b), the step of c) adding and reacting a compound, which reacts with a hydroxyl group other than a part of the hydroxyl groups and which becomes a source of the first spacer group and the hydroxyl group, to the system having the polyrotaxane obtained in the step b), to introduce the first spacer group and the hydroxyl group bound to the first spacer group, thereby to obtain the polyrotaxane having a hydroxyl value of 10 to 65 mgKOH/g.
12. The method according to claim 11 , wherein the first spacer group has a group derived from polycaprolactone.
13. The method according to claim 11 , wherein the first spacer group has a group derived from polycaprolactone and a group derived from hydroxypropyl.
14. The method according to claim 10 , wherein in the step a), the hydroxyl group is bound to a cyclic molecule via a second spacer group.
15. The method according to claim 14 , comprising, after the step b), the step of c) adding and reacting a compound, which reacts with a hydroxyl group other than a part of the hydroxyl groups and which becomes a source of the first spacer group and the hydroxyl group, to the system having the polyrotaxane obtained in the step b), to introduce the first spacer group and the hydroxyl group bound to the first spacer group, thereby to obtain the polyrotaxane having a hydroxyl value of 10 to 65 mgKOH/g.
16. The method according to claim 15 , wherein the second spacer group has a group derived from hydroxypropyl, and the third spacer group has a group derived from polycaprolactone.
17. The method according to claim 14 , wherein the second spacer group has a group derived from polycaprolactone.
18. The method according to claim 14 , wherein the second spacer group has a group derived from polycaprolactone and a group derived from hydroxypropyl.
19. The composition according to claim 1 , wherein the group having an ability to inactivate a hydroxyl group is selected from the group consisting of alkyl carbamoyl groups, wherein the alkyl of each of the alkyl carbamoyl groups independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and which inactivate a part of hydroxyl groups directly bound to a cyclic molecule.
20. The method according to claim 10 , wherein the hydroxyl group(s) is(are) directly bound to a cyclic molecule in the step a); and the group having an ability to inactivate a hydroxyl group is selected from the group consisting of alkyl carbamoyl groups, wherein the alkyl of each of the alkyl carbamoyl groups independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms.