ELASTOMER COMPOSITIONS COMPRISING AN ADDUCT BETWEEN AN SP2 HYBRIDIZED CARBON ALLOTROPE AND A DICARBOXYLIC ACID DERIVATIVE

Abstract

The present invention relates to elastomer compositions comprising adducts between compounds of formula (I) preferably derived from natural sources such as mucic, pyromucic, glucaric, glycaric, galactaric, muconic acid and/or linear derivatives thereof containing ester or amide groups and/or cyclic derivatives thereof with heteroatoms in the ring, such as oxygen or nitrogen, and carbon allotropes in which the carbon is sp.sup.2 hybridized, such as for example carbon nanotubes, graphene or nanographites, carbon black.

Claims

1. An elastomer composition comprising an adduct between an sp.sup.2 hybridized carbon allotrope and a compound of formula (I) ##STR00014## wherein the compound of formula (I) may be linear or cyclic and the symbol does not represent a bond when the compound is linear and represents a bond when the compound is cyclic, and X.sub.1, X.sub.2 X.sub.3, X.sub.4, X.sub.5 are selected independently from the group consisting of O, N—R.sub.7, halogen and S; and wherein if X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5 are halogen, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 are absent; and wherein: the compound of formula (I) is linear when: m and n are 1 and Y is selected from the group consisting of O, N—R.sub.7 and S; or m is 1 and n is 0 and Y is halogen and when the compound is linear, the symbols , and , represent independently a single or a double bond, and if the symbols and , are a double bond, v, u, p and q are 0; if the symbols and , are a single bond, v, u, p, q are 1; if the symbol is a double bond and the symbol is a single bond, v and p are 0 whereas u and q are 1; if the symbol is a double bond and the symbol is a single bond, v and p are 1 whereas u and q are 0; the compound of formula (I) is cyclic when: the symbols and are a double bond, and m and v are 0, and if Y is O, n is 0, or if Y is N, n is 1; and wherein: if X.sub.1 and Y are NR.sub.7 or S, then: R.sub.1, R.sub.6 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; if X.sub.1 and Y are O, then: R.sub.1, R.sub.6 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl, alkali metals, alkaline-earth metals, transition metals, or ##STR00015##  in which R.sub.8, R.sub.9, R.sub.10, R.sub.11 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; if X.sub.2 X.sub.3, X.sub.4, X.sub.5 are O, NR.sub.7 or S, then: R.sub.1, R.sub.6 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; R.sub.2, R.sub.3, R.sub.4, R.sub.5 are selected independently from the group consisting of: hydrogen, C.sub.2-C.sub.6 acyl, C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; and R.sub.7 is selected from the group consisting of: hydrogen, C.sub.2-C.sub.6 acyl, C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl.

2. The elastomer composition as claimed in claim 1, in which the compound of formula (I) is represented by formula (II) ##STR00016## in which X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5 are selected independently from the group consisting of O, N—R.sub.7, halogen and S; and in which if X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5 are halogen, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 are absent; and in which if n is 1, Y is selected from the group consisting of O, N—R.sub.7 and S; or if n is 0, Y is halogen, and in which the symbols and represent independently a single or a double bond, and if the symbols and are a double bond, v, p and q are 0, whereas if the symbols and , are a single bond, v, p, q are 1; and if the symbol is a double bond and the symbol is a single bond, v and p are 0 whereas u and q are 1; if the symbol is a double bond and the symbol is a single bond, v and p are 1 whereas u and q are 0; and in which: if X.sub.1 and Y are NR.sub.7 or S, then: R.sub.1, R.sub.6 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; if X.sub.1 and Y are O, then: R.sub.1, R.sub.6 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl, alkali metals, alkaline-earth metals, transition metals, or ##STR00017##  in which R.sub.8, R.sub.9, R.sub.10, R.sub.11 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; if X.sub.2 X.sub.3, X.sub.4, X.sub.5 are O, NR.sub.7 or S, then: R.sub.1, R.sub.6 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; R.sub.2, R.sub.3, R.sub.4, R.sub.5 are selected independently from the group consisting of: hydrogen, C.sub.2-C.sub.6 acyl, C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; and R.sub.7 is selected from the group consisting of: hydrogen, C.sub.2-C.sub.6 acyl, C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl.

3. The elastomer composition as claimed in claim 1, in which the compound of formula (I) is represented by formula (III) ##STR00018## in which X.sub.1, X.sub.2, X.sub.5 are selected independently from the group consisting of O, N—R.sub.7, halogen and S; and in which if X.sub.1, X.sub.2, X.sub.5 are halogen, R.sub.1, R.sub.2, R.sub.5 are absent; and if n is 1, Y is selected from the group consisting of O, N—R.sub.7 and S; or if n is 0, Y is halogen and in which: if X.sub.1 and Y are NR.sub.7 or S, then: R.sub.1, R.sub.6 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; if X.sub.1 and Y are O, then: R.sub.1, R.sub.6 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl, alkali metals, alkaline-earth metals, transition metals, or ##STR00019##  in which R.sub.8, R.sub.9, R.sub.10, R.sub.11 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; if X.sub.2 or X.sub.5 are O, NR.sub.7 or S, then: R.sub.1, R.sub.6 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; R.sub.2, R.sub.5 are selected independently from the group consisting of: hydrogen, C.sub.2-C.sub.6 acyl, C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; and R.sub.7 is selected from the group consisting of: hydrogen, C.sub.2-C.sub.6 acyl, C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl.

4. The elastomer composition as claimed in claim 1, in which the compound of formula (I) is represented by formula (IV) ##STR00020## in which X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5 are selected independently from the group consisting of O, N—R.sub.7, halogen and S; and in which if X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5 are halogen, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 are absent; and in which if n is 1, Y is selected from the group consisting of O, N—R.sub.7 and S; or if n is 0, Y is halogen and in which: if X.sub.1 and Y are NR.sub.S or S, then: R.sub.1, R.sub.6 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; if X.sub.1 and Y are 0, then: R.sub.1, R.sub.6 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl, alkali metals, alkaline-earth metals, transition metals, or ##STR00021##  in which R.sub.8, R.sub.9, R.sub.10, R.sub.11 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; if X.sub.2, X.sub.3, X.sub.4, X.sub.5 are O, NR.sub.7 or S, then: R.sub.1, R.sub.6 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; R.sub.2, R.sub.3, R.sub.4, R.sub.5 are independently selected from the group consisting of: hydrogen, C.sub.2-C.sub.6 acyl, C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; and R7 is selected from the group consisting of: hydrogen, C.sub.2-C.sub.6 acyl, C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl.

5. The elastomer composition as claimed in claim 1, wherein the compound of formula (I) is represented by formula (V) ##STR00022## wherein X.sub.1, X.sub.2, X.sub.4, X.sub.5 are selected independently from the group consisting of O, N—R.sub.7, halogen and S; and wherein if X.sub.1, X.sub.2, X.sub.4, X.sub.5 are halogen, R.sub.1, R.sub.2, R.sub.4, R.sub.5 are absent; and wherein if n is 1 and Y is selected from the group consisting of O, N—R.sub.7 and S; or if n is 0 and Y is halogen and wherein: if X.sub.1 and Y are NR.sub.7 or S, then: R.sub.1, R.sub.6 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; if X.sub.1 and Y are O, then: R.sub.1, R.sub.6 are selected independently from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl, alkali metals, alkaline-earth metals, transition metals, or ##STR00023##  wherein R.sub.8, R.sub.9, R.sub.10, R.sub.11 are independently selected from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; if X.sub.2, X.sub.4, X.sub.5 are O, NR.sub.7 or S, then: R.sub.1, R.sub.6 are independently selected from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; R.sub.2, R.sub.4, R.sub.5 are independently selected from the group consisting of: hydrogen, C.sub.2-C.sub.6 acyl, C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; and R.sub.7 is selected from the group consisting of: hydrogen, C.sub.2-C.sub.6 acyl, C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl.

6. The elastomer composition as claimed in claim 1, in which the compound of formula (I) is represented by formula (VI) ##STR00024## wherein X.sub.1, X.sub.2, X.sub.3, X.sub.5 are selected independently from the group consisting of O, N—R.sub.7, halogen and S; wherein if X.sub.1, X.sub.2, X.sub.3, X.sub.5 are halogen, R.sub.1, R.sub.2, R.sub.3, R.sub.5 are absent; and wherein if n is 1 and Y is selected from the group consisting of: O, N—R.sub.7 and S; or if n is 0 and Y is halogen, and in which: if X.sub.1 and Y are NR.sub.7 or S, then: R.sub.1, R.sub.6 are independently selected from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; if X.sub.i and Y are O, then: R.sub.1, R.sub.6 are independently selected from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl, alkali metals, alkaline-earth metals, transition metals, or ##STR00025##  in which R.sub.8, R.sub.9, R.sub.10, R.sub.11 are independently selected from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; if X.sub.2, X.sub.3, X.sub.5 are O, NR.sub.7 or S, then: R.sub.1, R.sub.6 are independently selected from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; R.sub.2, R.sub.3, R.sub.5 are independently selected from the group consisting of: hydrogen, C.sub.2-C.sub.6 acyl, C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; and R.sub.7 is selected from the group consisting of: hydrogen, C.sub.2-C.sub.6 acyl, C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl.

7. The elastomer composition as claimed in claim 1, in which the compound of formula (I) is represented by formula (VII) ##STR00026## wherein X.sub.1, X.sub.3, X.sub.4, X.sub.5 are selected independently from the group consisting of: O, N—R.sub.7, halogen and S; wherein if X.sub.1, X.sub.3, X.sub.4, X.sub.5 are halogen, R.sub.1, R.sub.3, R.sub.4, R.sub.5 are absent; if Y is O, n is 0, or if Y is N, n is 1; and wherein: if X.sub.1 is NR.sub.7 or S, then: R.sub.1, R.sub.6 are independently selected from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; if X.sub.1 is O, then: R.sub.1, R.sub.6 are independently selected from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl, alkali metals, alkaline-earth metals, transition metals, or ##STR00027##  in which R.sub.8, R.sub.9, R.sub.10, R.sub.11 are independently selected from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; if X.sub.3, X.sub.4, X.sub.5 are O, NR.sub.7 or S, then: R.sub.1, R.sub.6 are independently selected from the group consisting of: hydrogen, linear or branched C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; R.sub.3, R.sub.4, R.sub.5 are independently selected from the group consisting of: hydrogen, C.sub.2-C.sub.6 acyl, C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl; and R.sub.7 is selected from the group consisting of: hydrogen, C.sub.2-C.sub.6 acyl, C.sub.1-C.sub.6 alkyl, linear or branched C.sub.2-C.sub.6 alkenyl or alkynyl, aryl, linear or branched C.sub.1-C.sub.6 alkyl-aryl, linear or branched C.sub.2-C.sub.6 alkenyl-aryl, linear or branched C.sub.2-C.sub.6 alkynyl-aryl, heteroaryl.

8. The elastomer composition as claimed in any one of claims 1-7, wherein said sp.sup.2 hybridized carbon allotrope is selected from the group consisting of: carbon black, fullerene, single-wall or multi-walled carbon nanotubes, graphene, graphite with a number of graphene sheets between 2 and 10000.

9. The elastomer composition as claimed in any one of claims 1-8, wherein said carbon allotrope comprises functional groups selected from the group consisting of: oxygenated functional groups, preferably hydroxyls, epoxides; functional groups containing carbonyls, preferably aldehydes, ketones, carboxylic acids; functional groups containing nitrogen atoms, preferably amines, amides, nitriles, diazonium salts, imines; functional groups containing sulfur atoms, preferably sulfides, disulfides, mercaptans, sulfones, sulfinic and sulfonic groups.

10. The elastomer composition as claimed in claim 9, wherein said carbon allotrope is graphite oxide.

11. The elastomer composition as claimed in claim 9, wherein said carbon allotrope is graphene oxide.

12. The elastomer composition as claimed in any one of claims 1-11, wherein said compound of formula (I) is in the form of a salt and said alkali metals are selected from the group consisting of lithium, sodium, potassium; said alkaline-earth metals are selected from the group consisting of magnesium, calcium; said transition metals are rare earths, preferably neodymium.

Description

[0132] Some examples of preparation of the adduct comprising a compound of formula (I) and a carbon allotrope according to the present invention will be described below.

[0133] These examples will also be illustrated with reference to the appended drawings; in which:

[0134] FIG. 1 shows the .sup.1H-NMR spectrum [400 MHz in DMSO-d.sub.6 (*)] of 3,4,5-triacetoxy-6-oxo-tetrahydro-pyran-2-carboxylic acid (1);

[0135] FIG. 2 shows the .sup.1H-NMR spectrum [400 MHz in D.sub.2O (*)] of 5-acetoxy-6-oxo-6H-pyran-2-carboxylic acid (2);

[0136] FIG. 3 shows the .sup.1H-NMR spectrum [400 MHz in CDCl.sub.3 (*)] of the ethyl ester of 5-hydroxy-6-oxo-6H-pyran-2-carboxylic acid (3);

[0137] FIG. 4 shows the aqueous suspensions of adducts according to the invention;

[0138] FIG. 5 shows the X-ray profiles (WAXD patterns) of HSAG, CNT, of adducts according to the invention;

[0139] FIG. 6 shows the FT-IR spectra of adducts according to the invention;

[0140] FIG. 7 shows the FT-IR spectra of adducts according to the invention;

[0141] FIG. 8 shows the HRTEM images of adducts according to the invention;

[0142] FIGS. 9a-c show the UV-VIS MEASUREMENTS of suspensions of adducts according to the invention;

[0143] FIGS. 10a-c show the UV-VIS MEASUREMENTS the stability over time of suspensions of adducts according to the invention;

[0144] FIG. 11 shows the UV-VIS MEASUREMENTS of the absorbance-wavelength relation of adducts according to the invention.

EXAMPLES

[0145] All the chemicals used in the syntheses given in the following examples were purchased from: mucic acid (Aldrich), acetic anhydride (Aldrich), acetone (Aldrich), sodium acetate trihydrate (Carlo Erba reagenti). It should be pointed out that mucic acid is derived from a monosaccharide, galactose, which is of natural origin.

[0146] The multi-walled carbon nanotubes (MWCNT or CNT) (NC7000 series) were purchased from NANOCYL™ Inc (www.nanocyl.com) and used as supplied by the seller.

[0147] The graphites used in the present invention were purchased from Asbury Graphite Mills Inc. The following commercial grades were used: Synthetic Graphite 8427® (HSAG), NG24, NG27, NG307, G3806, SFG6,G3807. The carbon black (CB) used in the present invention was acquired from Cabot. The following commercial grades were selected: CB N326, CB N234, CB N115(CB).

[0148] The adducts obtained in the examples presented hereunder were analyzed as follows:

[0149] .sup.1H-NMR and .sup.13C-NMR the .sup.1H-NMR and .sup.13C-NMR spectra were recorded with a Bruker 400 MHz instrument (100 MHz .sup.13C) operating at 298 K. The chemical shifts are given in parts per million (ppm) with the peaks of the solvent residues as internal standard (DMSO-d6: δ.sub.H=2.50 ppm, CDCl.sub.3: δ.sub.H=7.26 ppm).

[0150] X-rays (Powder X-ray Diffraction)

[0151] the X-ray profiles (Wide-angle X-ray diffraction (WAXD)) were obtained in rereflection, using a diffractometer “automatic Bruker D8 Advance diffractometer, with nickel filtered Cu—Kα radiation”). The profiles were recorded in the range of 28 between 10° and 100°.

[0152] Thermogravimetric Analysis (TGA)

[0153] Thermogravimetric analysis (TGA tests) under a stream of N.sub.2 (60 mL/min) was carried out using a Mettler TGA SDTA/851 instrument according to standard method ISO9924-1. The samples (10 mg) were heated from 30 to 300° C. at 10° C./min, holding at 300° C. for 10 min, and immediately thereafter heating to 550° C. (20° C./min). After holding them at 550° C. for 15 min, they are heated further to 650° C. at a rate of 30° C./min and held at 650° C. for 20 min under an air stream (60 mL/min).

[0154] FT-IR

[0155] The IR spectra were recorded in transmission (128 scans and 4 cm.sup.−1 resolution) on diamond crystal (diamond anvil cell (DAC)) using a ThermoElectron FT-IR Continupm IR microscope.

[0156] The HRTEM images were obtained using a “Philips CM 200 field emission gun microscope” operating with a voltage of 200 kV. A few drops of the suspension were deposited on a grid (carbon-coated copper grid) of 200 mesh and dried for several hours prior to analysis. During acquisition of the HRTEM images, the sample did not undergo structural changes.

[0157] For measurement of UV-visible absorption, suspensions of the adducts (2 mL) were taken by Pasteur pipette and transferred to 1-cm quartz cuvettes (volume 1 or 3 mL) and analyzed using a Hewlett Packard 8452A Diode Array Spectrophotometer. The blank of the solvent used was recorded.

[0158] Determination of the Functionalization Yield

[0159] “Functionalization yield” means the quantity in wt % of molecule bound to the carbon allotrope with sp.sup.2 hybridization. The functionalization yield of the adducts obtained according to the examples given in this description was calculated using the following equation, in which, as stated above, CA denotes carbon allotrope or carbon-containing substance:

[00001]$\mathrm{Functionalization}\mathrm{yield}\left(\%\right)=100\star \frac{\begin{array}{c}\mathrm{Compound}\mathrm{of}\mathrm{formula}\left(l\right)\mathrm{by}\mathrm{weight}\mathrm{in}\\ \left(CA-\mathrm{Compound}\mathrm{of}\mathrm{formula}\left(l\right)\mathrm{adduct}\right)\mathrm{after}\mathrm{purification}\end{array}}{\begin{array}{c}\mathrm{Compound}\mathrm{of}\mathrm{formula}\left(l\right)\mathrm{by}\mathrm{weight}\mathrm{in}\\ \left(CA-\mathrm{Compound}\mathrm{of}\mathrm{formula}\left(l\right)\mathrm{adduct}\right)\mathrm{before}\mathrm{purification}\end{array}}$

[0160] The values given for the purposes of the calculation of the yield refer to the quantity of the compound of formula (I) found by TGA before and after the purification step and refer to the losses (in wt %) found from the TGA plot in the temperature range from 0 to 700° C.

[0161] Hereinafter in the present description, the term “yield” means the functionalization yield, unless stated otherwise.

Examples 1-3. Synthesis of the Precursor of Pyrone and of Pyrones Example 1. Synthesis of 3,4,5-triacetoxy-6-oxo-tetrahydro-pyran-2-carboxylic acid (1) (Precursor)

[0162] ##STR00009##

[0163] A 100-mL flask equipped with a magnetic stirrer and a condenser is charged with 10 g of mucic acid (0.049 mol) and 51 mL of acetic anhydride (0.54 mol). The mixture was stirred at 130° C. overnight. The pure product was isolated by filtration.

[0164] The product was characterized by NMR spectroscopy: .sup.1H NMR (400MHz, DMSO-d6, δ in ppm): 2.08 (s, 3H); 2.15 (s, 6H); 5.01 (dd, 1H); 5.27 (d, 1H); 5.51 (t, 1H); 5.89 (d, 1H); 12.10 (s, 1H) as shown in FIG. 1.

[0165] In particular, in the spectrum of the reaction mixture given in FIG. 1, attention should be paid to the signals due to 3,4,5-triacetoxy-6-oxo-tetrahydro-pyran-2-carboxylic acid (1), at excess of acetic anhydride and acetic acid. The .sup.1H NMR spectrum, with the relevant attributions, confirms the structural formula shown in the figure.

[0166] The synthesis yield is 99% with an atom economy (AE) of 77% and a reaction mass efficiency (RME) of 76%.

Example 2. Synthesis of 5-acetoxy-6-oxo-6H-pyran-2-carboxylic acid

[0167] ##STR00010##

[0168] A 100-mL flask equipped with a magnetic stirrer and a condenser is charged with 1 g of CH.sub.3COONa.3H.sub.2O (0.049 mol) and the reaction mixture obtained in example 1. The new reaction mixture is then stirred for 12 hours at 100° C. At the end of this time, HCl solution (0.0002 mol; 2 ml; 36%) is added and a few minutes after addition it is noted that there is formation of a white precipitate (59.8 g). Once formed, the precipitate is removed by filtration. The solution, on the other hand, is concentrated at reduced pressure until about 32 g of solution is obtained. The solution thus obtained is left to stand until a new precipitate has formed. After 1 day, the procedure is repeated and a further 3.2 g of solid is isolated. The solid product of the 3 filtrations was characterized by NMR spectroscopy.

[0169] The product was characterized by .sup.1H NMR spectroscopy (400 MHz, DMSO-d6, δ in ppm): 2.27 (s, 3H); 7.13 (d, 1H); 7.47 (d, 1H); 12.10 (s, 1H) as shown in FIG. 2.

[0170] In particular, in the spectrum of the reaction mixture given in FIG. 2, attention should be paid to the signals due to 5-acetoxy-6-oxo-6H-pyran-2-carboxylic acid (2): the doublets due to the hydrogens H4 and H5 are at 7.13 and 7.47 ppm and are in line with the chemical structure given in FIG. 2. The .sup.1H NMR spectrum, with the relevant attributions, confirms the structural formula shown in the figure.

[0171] The synthesis yield is 65% with an atom economy (AE) of 62% and a reaction mass efficiency (RME) of 41%.

Example 3. Synthesis of the ethyl ester of 5-hydroxy-6-oxo-6H-pyran-2-carboxylic acid (3)

[0172] ##STR00011##

[0173] A 100-mL flask equipped with a magnetic stirrer and a condenser is charged with the product obtained in example 2 (2) (3.1 g), ethanol (30 ml) and six drops of sulfuric acid (1.0 g; 0.049 mol). The mixture thus obtained is stirred at 85° C. overnight. At the end of this time, the reaction mixture is poured into a separatory funnel and water is added (180 ml) and a small amount of sodium bicarbonate so as to bring the pH to neutral. The mixture is extracted 3 times with dichloromethane (60 ml). The residual water is basified with sodium bicarbonate. The organic phases are dried over sodium sulfate and then filtered and dried thoroughly at reduced pressure.

[0174] The product was characterized by .sup.1H NMR spectroscopy (400 MHz, CDCl.sub.3-d6, δ in ppm): 1.40 (t, 3H); 4.40 (q, 2H); 6.78 (d, 1H); 7.20 (d, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3): δ 14.17, 62.17, 112.93, 113.00, 140.85, 145.70, 159.14, 159.59 ppm) as shown in FIG. 3.

[0175] The signals due to the ethyl ester of 5-hydroxy-6-oxo-6H-pyran-2-carboxylic acid (3) are clearly present in the spectrum in FIG. 3 and are in line with the chemical structure shown. The .sup.1H NMR spectrum, with the relevant attributions, confirms the structural formula shown in the figure.

[0176] The synthesis yield is 99% with an atom economy (AE) of 63% and a reaction mass efficiency (RME) of 41%.

Examples 4-12. Preparation of Adducts of a Pyrone with High Surface Area Graphite (HSAG)

Example 4. Preparation of a Physical Mixture between the Product of Example 2 and High Surface Area Graphite (HSAG)

[0177] In this example and in some subsequent examples, the mmols of graphite are indicated, which are calculated as the theoretical mmols of benzene rings without hydrogen. Where, in the subsequent examples, the mmols of carbon allotropes are given, they have been calculated in the same way.

[0178] High surface area graphite (HSAG) (100 mg, 72 mmol), compound 2 (100 mg, 1.3 mmol) and acetone (10 ml) are poured successively into a 50-mL single-neck flask. The mixture obtained is unstable and is therefore sonicated for 15 minutes using a 2L ultrasonic bath. After this time the solvent is removed at reduced pressure. 200 mg of HSAG/2 physical mixture was obtained.

Example 5. Preparation of an Adduct between the Product of Example 2 and High Surface Area Graphite (HSAG)

[0179] The physical mixture obtained in example 4 (50 mg) was poured into a flask and was heated at 130° C. for 2 hours. The powder thus obtained was analyzed. 45 mg of HSAG/2-T adduct was obtained.

Example 6. Preparation of an Adduct between the Product of Example 2 and High Surface Area Graphite (HSAG)

[0180] The physical mixture obtained in example 4 (50 mg) was poured into a flask and was heated at 160° C. for 2 hours. The powder thus obtained was analyzed. 40 mg of HSAG/2-T adduct was obtained.

Example 7. Preparation of a Physical Mixture between the Product of Example 3 and High Surface Area Graphite (HSAG)

[0181] High surface area graphite HSAG (1.8 g, 26.2 mmol), the product of example 3 (0.48 g, 2.62 mmol) and acetone (10 ml) are poured successively into a 100-mL single-neck flask. The mixture obtained is unstable and is therefore sonicated for 30 minutes using a 2 L ultrasonic bath. After this time the solvent is removed at reduced pressure. 2.2 g of HSAG/3 physical mixture was obtained.

Example 8. Preparation of an Adduct between the Product of Example 3 and High Surface Area Graphite (HSAG)

[0182] The physical mixture obtained in example 7 (400 mg) was poured into a flask and was heated at 110° C. for 8 hours. The black powder thus obtained was filtered on a Buchner and was washed with acetone (30 mL×3). The final yield is equal to 81%.

Example 9. Preparation of an Adduct between the Product of Example 3 and High Surface Area Graphite (HSAG)

[0183] The physical mixture obtained in example 7 (400 mg) was poured into a flask and heated at 130° C. for 8 hours. The black powder thus obtained was filtered on a Buchner and was washed with acetone (30 mL×3). The final yield is equal to 83.4%.

Example 10. Preparation of an Adduct between the Product of Example 3 and High Surface Area Graphite (HSAG)

[0184] The physical mixture obtained in example 7 (400 mg) was poured into a flask and heated at 150° C. for 8 hours. The black powder thus obtained was filtered on a Buchner and was washed with acetone (30 mL×3). The final yield is equal to 81.5%.

Example 11. Preparation of an Adduct between the Product of Example 3 and High Surface Area Graphite (HSAG)

[0185] The physical mixture obtained in example 7 (400 mg) was poured into a flask and heated at 160° C. for 8 hours. The black powder thus obtained was filtered on a Buchner and was washed with acetone (30 mL×3). The final yield is equal to 91%.

[0186] FIG. 4 shows aqueous suspensions of the adduct of example 11 at various concentrations (1 mg/mL, 0.5 mg/mL, 0.3 mg/mL, 0.1 mg/mL, 0.05 mg/mL, 0.01 mg/mL, 0.005 mg/mL). The increase in concentration of the dispersions, passing from 0.005 mg/mL to 1 mg/mL, is observed qualitatively in FIG. 4.

Example 12. Preparation of an Adduct between the Product of Example 3 and High Surface Area Graphite (HSAG)

[0187] The physical mixture obtained in example 7 (1 g) was poured into a jar in a Retsch S100 planetary ball mill, with the grinding jar moving in a horizontal plane, with a volume of 0.3 L. The jar was rotated at 300 rpm for 8 hours at room temperature. The black powder thus obtained was filtered on a Buchner and was washed with acetone (30 mL×3). The final yield is equal to 85.2%.

Examples 13-14. Preparation of Adducts of a Pyrone with Carbon Nanotubes (CNTs)

Example 13. Preparation of a Physical Mixture between the Product of Example 3 and Carbon Nanotubes (CNTs)

[0188] CNTs (1.8 g, 26.2 mmol), the product of example 3 (0.48 g, 2.62 mmol) and acetone (10 ml) are poured successively into a 100-mL single-neck flask. The mixture obtained is unstable and is therefore sonicated for 30 minutes using a 2 L ultrasonic bath. After this time the solvent is removed at reduced pressure. 2.0 g of CNT/3 physical mixture was obtained.

Example 14. Preparation of an Adduct between the Product of of Example 3 and Carbon Nanotubes (CNTs)

[0189] The physical mixture obtained in example 13 (0.4 g) was poured into a flask and heated at 160° C. for 8 hours. The black powder thus obtained was filtered on a Buchner and was washed with acetone (30 mL×3). The final yield is equal to 96%.

[0190] FIG. 5 shows the X-ray profiles (WAXD patterns) of HSAG, CNTs and the adducts from examples 11, 12 and 14. The X-ray profiles of graphite (HSAG) and carbon nanotubes (CNTs) both show the presence of the (00) reflection: 002 at 26.6° (2θ) relating to the crystalline order in the direction orthogonal to the stacked layers. In both profiles it is possible to assign the reflections to 100 and 110, at 42.5° and 77.6° (2θ), respectively. The number of stacked layers was estimated by applying the Scherrer equation to the 002 rereflection at about 35 for HSAG and 12 for the CNTs. With regard to the samples of graphite and carbon nanotubes functionalized with pyrone 3, it was found that in all cases the reflections already assigned for the starting allotropes, were found at the same values of 28, indicating that formation of the adducts did not promote expansion of the distance between the layers. The number of stacked layers in the adducts of HSAG and CNT with compound 3 was calculated by applying the Scherrer equation to the 002 reflection. From the calculation, the HSAG/3 and HSAG/3 T samples show 21 and 31 superposed layers, respectively. The adduct CNT/3 shows 10 stacked crystal layers.

[0191] FIG. 6 shows the FT-IR spectra of the compound obtained as from example 3, HSAG and of the adducts from examples 4, 12, 11.

[0192] All the spectra in FIG. 6 are characterized by increasing absorption at higher wavenumbers due to phenomena of scattering/rereflection of the incident IR light from part of the particles that make up the sample. The FT-IR spectrum of HSAG is characterized by a very intense band at 1569 cm.sup.−1, relating to the collective C═C stretching vibration typical of the graphene materials. In both spectra of the HSAG/3 T and HSAG/3 adducts, the C═C peak is detectable together with other bands relating to new functional groups. The corresponding peaks are located at: i) 730 cm.sup.−1, C═C vibrations; ii) 1210 cm.sup.−1, C—O stretching vibrations and iii) 1729 cm.sup.−1 C═O.

[0193] The spectrum relating to the physical mixture (HSAG/3) shows characteristic bands of pyrone 3 and of the starting graphite. In the spectrum of pyrone 3 there are two very intense bands at 1745 cm.sup.−1 and 1698 cm.sup.−1 relating to the stretching vibrations of the two carbonyls (C═O) of pyrone 3. In the spectra of the HSAG/3 adducts, these two bands have disappeared and the presence of a new band is detected at 1729 cm.sup.−1.

[0194] FIG. 7 shows the FT-IR spectra of the compound obtained as from example 3, CNT and adducts from examples 13, 14.

[0195] All the spectra in FIG. 7 are characterized by increasing absorption at higher wavenumbers due to phenomena of scattering/rereflection of the incident IR light from part of the particles that make up the sample. The FT-IR spectrum of the starting carbon nanotube (CNT) is characterized by a very intense band at 1569 cm.sup.−1, relating to the collective C═C stretching vibration typical of the graphene materials. In the spectrum of the CNT/3 adduct, the C═C peak is detectable together with other bands relating to new functional groups. The corresponding peaks are located at: i) 730 cm.sup.−1, C═C vibrations; ii) 1210 cm.sup.−1, C—O stretching vibration and iii) 1729 cm.sup.−1 C═O.

[0196] The spectrum relating to the physical mixture (CNT/3) shows characteristic bands of pyrone 3 and of the starting graphite. In the spectrum of pyrone 3 there are two very intense bands at 1745 cm.sup.-1 and 1698 cm.sup.−1 relating to the stretching vibrations of the two carbonyls (C═O) of pyrone 3. In the spectra of the CNT/3 adducts, these two bands have disappeared and the presence of a new band is detected at 1729 cm.sup.−1.

[0197] FIG. 8 shows HRTEM images of the CNTs (b), of the adduct from example 13 (d) 11 (f), 12 (h) isolated from the supernatant after centrifugation for 30 min at 6000 rpm. (Bright field TEM micrographs at low magnification (a, c, e, g))

[0198] The starting CNTs shown in the figure seem to be agglomerated (entangled) (FIG. 8a). The high-resolution micrographs of the suspensions of CNT 3 adduct show that functionalization seems to improve dispersion of the carbon nanotube in water and seems to promote untangling thereof (FIG. 8c).

[0199] In FIG. 8d it can be seen that the surface of the carbon nanotube has been altered considerably after functionalization with compound 3. FIGS. 8e and 8g also show the TEM micrographs relating to the suspensions of the adduct HSAG with compound 3. It appears from the micrographs that the number of stacked graphene sheets has decreased. The micrographs at higher magnification in FIG. 8f and h reveal the presence of small numbers of superposed graphite layers. It would appear that formation of the HSAG/3 adduct leads to a reduction of the number of stacked layers. In both HSAG/3 adducts it is found that the lateral dimension of the graphene sheets is maintained. FIG. 8f shows nanographites that range from 9 to 20 superposed graphene sheets (indicated in the boxes). In FIG. 8h, we may note the presence of isolated nanographites, in particular with 3 or 4 superposed graphene sheets.

Example 15. Preparation of an Adduct between the Product of Example 3 and NG24 Graphite (Thermal Treatment at 180° C.)

[0200] First the NG24 graphite (1.8 g, 26.2 mmol), the product of example 3 (0.48 g, 2.62 mmol) and acetone (10 ml) are poured into a 100-mL flask. The mixture thus obtained is sonicated for 30 min, using a 2 L bench sonicator. At the end of this time the solvent is removed at reduced pressure. The physical mixture obtained is heated at 180° C. for 3 hours. The powder obtained is washed with acetone (30 mL×3) and then filtered on a Buchner. The final yield of adduct is 75.7%.

Example 16. Preparation of an Adduct between the Product of Example 3 and NG24 Graphite (Thermal Treatment at 110° C.)

[0201] The mixture is prepared as in example 15 but the thermal treatment is carried out at 110° C., with a final yield of adduct of 23%.

Example 17. Preparation of an Adduct between the Product of Example 3 and NG24 Graphite (Thermal Treatment at 130° C.)

[0202] The mixture is prepared as in example 15 but the thermal treatment is carried out at 130° C., with a final yield of adduct of 24%.

Example 18. Preparation of an Adduct between the Product of Example 3 and NG24 Graphite (Thermal Treatment at 150° C.)

[0203] The mixture is prepared as in example 15 but the thermal treatment is carried out at 150° C., with a final yield of adduct of 44%.

Example 19. Preparation of an Adduct between the Product of Example 3 and NG24 Graphite (Thermal Treatment at 160° C.)

[0204] The mixture is prepared as in example 15 but the thermal treatment is carried out at 160° C., with a final yield of adduct of 62.5%.

Example 20. Preparation of an Adduct between the Product of Example 3 and NG24 Graphite (Thermal Treatment at 200° C.)

[0205] The mixture is prepared as in example 15 but the thermal treatment is carried out at 200° C., with a final yield of adduct of 62.9%.

Example 21. Preparation of an Adduct between the Product of Example 3 and NG24 Graphite (Mechanical Treatment)

[0206] The mixture is prepared as in example 15 but the treatment is carried out using a ball mill: planetary ball mill S100 (Retsch) equipped with a jar movable in the horizontal plane (volume=0.3 L). The jar rotated at 300 rpm, at room temperature for 3 hours. The powder thus obtained was purified using acetone (3×30 mL) and filtered on a Buchner. Final yield of adduct=23%.

Example 22. Preparation of an Adduct between the Product of Example 3 and NG27 Graphite (Thermal Treatment at 160° C.)

[0207] The mixture is prepared as in example 15 at a temperature of 160° C. and using NG27 graphite, with a final yield of adduct of 47.5%.

Example 23. Preparation of an Adduct between the Product of Example 3 and NG27 Graphite (Thermal Treatment at 160° C.)

[0208] The mixture is prepared as in example 22 at a temperature of 160° C., using an amount of product of example 3 equal to 3 mol %. Final yield of adduct=72.3%.

Example 24. Preparation of an Adduct between the Product of Example 3 and NG307 Graphite (Thermal Treatment at 160° C.)

[0209] The mixture is prepared as in example 15 at a temperature of 160° C. and using NG307 graphite, with a final yield of adduct of 63.3%.

Example 25. Preparation of an Adduct between the Product of Example 3 and NG307 Graphite (Thermal Treatment at 160° C.)

[0210] The mixture is prepared as in example 24 at a temperature of 160° C., using an amount of product of example 3 equal to 3 mol %. Final yield of adduct=83%.

Example 26. Preparation of an Adduct between the Product of Example 3 and SFG6 Graphite (Thermal Treatment at 160° C.)

[0211] The mixture is prepared as in example 15 at a temperature of 160° C. and using SFG6 graphite, with a final yield of adduct of 3.6%.

Example 27. Preparation of an Adduct between the Product of Example 3 and G3806 Graphite (Thermal Treatment at 160° C.)

[0212] The mixture is prepared as in example 15 at a temperature of 160° C. and using G3806 graphite, with a final yield of adduct of 19.7%.

Example 28. Preparation of an Adduct between the Product of Example 3 and G3807 Graphite (Thermal Treatment at 160° C.)

[0213] The mixture is prepared as in example 15 at a temperature of 160° C. and using G3807 graphite, with a final yield of adduct of 12%.

Example 29. Preparation of an Adduct between the Product of Example 3 and CB N326 carbon black (thermal treatment at 160° C.)

[0214] The mixture is prepared as in example 15 at a temperature of 160° C. and using CB N326 carbon black, with a final yield of adduct of 19.1%.

Example 30. Preparation of an Adduct between the Product of Example 3 and CB N326 carbon black (thermal treatment at 160° C.)

[0215] The mixture is prepared as in example 29 at a temperature of 160° C., using an amount of product of example 3 equal to 3 mol%. Final yield of adduct =50%.

Example 31. Preparation of an Adduct between the Product of Example 3 and CB N234 carbon black (thermal treatment at 160° C.)

[0216] The mixture is prepared as in example 15 at a temperature of 160° C. and using CB N234 carbon black, with a final yield of adduct of 35%.

Example 32. Preparation of an Adduct between the Product of Example 3 and CB N234 carbon black (thermal treatment at 160° C.)

[0217] The mixture is prepared as in example 32 at a temperature of 160° C., using an amount of product of example 3 equal to 3 mol%. Final yield of adduct =62%.

Example 33. Preparation of an Adduct between the Product of Example 3 and CB N115 carbon black (thermal treatment at 160° C.)

[0218] The mixture is prepared as in example 15 at a temperature of 160° C. and using CB N115 carbon black, with a final yield of adduct of 41%.

Example 34. Preparation of an Adduct between the Product of Example 3 and CB N115 Carbon Black (Thermal Treatment at 160° C.)

[0219] The mixture is prepared as in example 33 at a temperature of 160° C., using an amount of product of example 3 equal to 3 mol %. Final yield of adduct=67%.

Examples 35-38

Aqueous Suspensions of Adducts of a Pyrone with Carbon Allotropes

Example 35. Aqueous Suspension of the Product of Example 11, Adduct between the Product of Example 3 and High Surface Area Graphite (HSAG)

[0220] Water is added to an aliquot of the powder obtained in example 11: suspensions at various concentrations were obtained: 1 mg/mL; 0.5 mg/mL; 0.3 mg/mL; 0.1 mg/mL; 0.05 mg/mL; 0.01 mg/mL; 0.05 mg/mL. Each suspension was sonicated for 10 minutes in a 2 L ultrasonic bath (at 260 W) and then UV-Vis absorption was measured immediately after sonication, after 2, 5, 24 hours and 7 days. The suspension at 1 mg/mL (10 mL) was poured into a Falcon™ (15 mL) and centrifuged at 6000 rpm for 30 minutes. The UV-Vis absorption was measured immediately after each centrifugation.

Example 36. Aqueous Suspension of the Product of Example 8, Adduct between the Product of Example 3 and High Surface Area Graphite (HSAG)

[0221] The aqueous suspensions were prepared as described in example 35.

Example 37. Aqueous Suspension of the Product of Example 9, Adduct between the Product of Example 3 and High Surface Area Graphite (HSAG)

[0222] The aqueous suspensions were prepared as described in example 35.

[0223] FIGS. 9a-c show UV-VIS measurements of the suspensions prepared as in examples 35, 36 and 37. The Absorbance-Concentration Relation is shown, i.e. the correlation between the absorbance (on the ordinate) and the concentration (on the abscissa).

[0224] FIGS. 10a-c show UV-VIS measurements of the suspensions prepared as in examples 35, 36 and 37. The stability over time is shown, i.e.: the absorbance of suspensions that have a concentration equal to 1 mg/mL, measured at different times after sonication.

Example 38. Aqueous Suspension of the Product of Example 14, Adduct between the Product of Example 3 and Carbon Nanotubes (CNTs)

[0225] Water is added to an aliquot of the powder obtained in example 14: suspensions at various concentrations were obtained: 1 mg/mL; 0.5 mg/mL; 0.3 mg/mL; 0.1 mg/mL; 0.05 mg/mL; 0.01 mg/mL; 0.05 mg/mL. Each suspension was sonicated for 10 minutes in a 2 L ultrasonic bath (at 260 W) and then UV-Vis absorption was measured immediately after sonication, after 2, 5, 24 hours and 7 days. FIG. 11 shows UV-VIS measurements of the suspension prepared as in example 38 at 1 mg/mL. In particular, FIG. 11 shows the correlation between absorbance and wavelength, which is typically supplied by a UV-Vis spectrum.

Example 39. Synthesis of the ethyl ester of dihydroxymuconic acid

[0226] ##STR00012##

[0227] The diester was prepared according to the procedure of Fischer and Speier from mucic acid using anhydrous ethanol and HCl. [Fischer and Speier, Ber., 28, 3252 (1895)]

[0228] A 100-mL flask equipped with a magnetic stirrer and a condenser is charged with 10 g of diester of mucic acid and 60 mL of acetic anhydride, in the absence of other chemical individuals. The mixture was stirred at 130° C. overnight. In this first reaction step, the acetic anhydride reacts with the hydroxyls of the ester of mucic acid, causing the acetylation reaction. The acetic anhydride also functions as a solvent. The product is isolated by filtration. Once obtained, the product is poured into a 100-mL flask equipped with a magnetic stirrer and a condenser and 1 g of CH.sub.3COONa.3H.sub.2O is added. The new reaction mixture is then stirred for 12 hours at 100° C. At the end of this time, HCl solution is added, and a few minutes after addition it is noted that there is formation of a white precipitate. Once formed, the precipitate is removed by filtration.

Example 40. Preparation of an Adduct between the Product of Example 39 and High Surface Area Graphite (HSAG)

[0229] 1 g of graphite and 200 mg of the product of example 39 are poured successively into a 100-mL single-neck flask containing 50 mL of acetone. The acetone is then removed at reduced pressure. The mixture is heated at 160° C. for 3 hours. At the end of this treatment, the solid is purified by extraction with acetone in a Soxhlet extractor.

[0230] The purified solid was suspended in water (1 mg/1 mL of water). The suspension was sonicated with a bench sonicator for 10 minutes. The suspension proved to be stable for at least 7 days.

Example 41. Synthesis of N.SUP.1.,N.SUP.6.-dihexyl-2,3,4,5-tetrahydroxyhexanediamide

[0231] ##STR00013##

[0232] Mucic acid (5 g) and dimethylsulfoxide (10 mL) are poured into a 100-mL single-neck flask. The mixture is stirred at 140° C. for 20 minutes. At the end of this time the mixture is cooled to room temperature. Hexanamine (2 equivalents) is added at this temperature. It is stirred at 100° C. for two hours.

[0233] The product is isolated by filtration and is a white solid.

Example 42. Preparation of a Physical Mixture between the Product of Example 41 and High Surface Area Graphite (HSAG)

[0234] The graphite and the product of example 41 are poured successively into a 100-mL single-neck flask. Water is added to the mixture and it is sonicated for 30 minutes. The suspension thus obtained proves to be stable for 24 hours.

Example 43 (Comparison). Elastomer Compound with Carbon Black as Reinforcing Filler

[0235] In the following description, phr signifies parts per hundred rubber, i.e. parts per 100 parts of rubber.

[0236] The compound was prepared in an internal mixer of the Brabender® type having a mixing chamber with a volume equal to 50 cc, reaching, with all the ingredients fed in, a degree of filling equal to 80%.

[0237] 100 phr of natural rubber, commercial grade NR-RSS3, was put in the mixer, and mastication was carried out at 80° C. for 1 minute. Then 60 phr of CB N234 black was added, mixing for a further 5 minutes and discharging the composite obtained at 100° C. The composite thus prepared was then put in the internal mixer at 80° C., adding 2 phr of ZnO (from Zincol Ossidi), 2 phr of stearic acid (from Aldrich), 2 phr of paraphenylenediamine, mixing for 2 minutes. Then 1.20 phr of sulfur (from Solfotecnica) and 1.70 phr of N-tert-butyl-2-benzothiazyl sulfenamide (TBBS) (from Flexsys) were added, mixing for a further 2 minutes. The composite was discharged at 90° C.

Example 44. Elastomer Compound with Adduct According to Example 31 as Reinforcing Filler

[0238] The compound was prepared according to the preparation in example 43; the carbon black used for preparation had been treated beforehand with the compound prepared in example 3. The procedure for preparing the adduct of CB N234 with the compound prepared in example 3 is as given in example 31.

Dynamic-Mechanical Characterization of the Composites from Examples 43 and 44

[0239] Dynamic-mechanical characterization is carried out by the so-called strain sweep test.

[0240] The composites of examples 43 and 44 are vulcanized at 151° C. for 30 minutes. The value of the shear storage modulus is then measured, by applying a sinusoidal stress at 50° C. and a frequency of 1 Hz, in a range of strain amplitude between 0.1% and 25%, using the Monsanto R.P.A. 2000 rheometer.

[0241] Operating conditions: The specimens were held in the instrument at 50° C. for 90 seconds, the stress was then applied at 50° C. in the range of strain amplitude between 0.1% and 25%, with a frequency of 1 Hz, increasing the strain amplitude in the range stated above. This treatment is carried out to cancel the previous thermo-mechanical history. Application of the stress is then repeated in the same experimental conditions. Vulcanization was then carried out at 150° C. for 30 minutes, with a frequency of 1.667 Hz and an angle of 6.98% (0.5 rad). The vulcanized specimen was left in the instrument for 10 minutes at 50° C. Sinusoidal stress was then applied in the same conditions stated above, then leaving the specimen in the instrument for 10 minutes at 50° C. Sinusoidal stress is then applied again, still in the same experimental conditions. Table 1 shows the values of G′.sub.γ=0.28%, ΔG′, G″max and (Tan Delta).sub.max determined by the strain sweep test for the composites of Example 43 and of Example 44. The values presented in Table 1 demonstrate that there is a reduction of the Payne effect of the composite when a carbon black modified with a compound according to the invention is used.

TABLE-US-00001 TABLE 1 Example of preparation of Ex. Ex. compound 43 44 G′.sub.y=0.28% MPa 6.58 5.85 ΔG′ MPa 4.98 4.25 G″.sub.max MPa 0.85 0.71 (Tan Delta).sub.max — 0.27 0.24 G′.sub.y=0.28% = value of G′ measured at 0.28%. ΔG′ = difference between the value of G′ at minimum strain and the value of G′ measured at the maximum strain reached. G″.sub.max = maximum value of G″ observed on the curve of G″. (Tan Delta).sub.max = maximum value of Tan Delta observed on the curve.