A method of carrying out a metathesis reaction includes the combination of at least one alkene or non conjugated diene with a Ruthenium-based catalyst with an cyclic(alkyl)(amino)carbene ligand to form a reaction mixture, heating the reaction mixture to a temperature of 100° C. or greater in the absence of a solvent in bulk conditions, and mechanically stirring the reaction mixture. The reaction can be an ADMET, ROMP, a metathesis ring-closure or an olefin exchange reaction.

The present invention provides a modifier, a modified and conjugated diene-based polymer which is modified using the same, and a rubber composition including the modified and conjugated diene-based polymer, and more particularly, a modifier which includes a compound represented by Formula 1 and is capable of improving the mixing properties between a conjugated diene-based polymer and a filler, a modified and conjugated diene-based polymer which is modified using the same, and a rubber composition including the modified and conjugated diene-based polymer.

The present invention provides a modifier, a modified and conjugated diene-based polymer which is modified using the same, and a rubber composition including the modified and conjugated diene-based polymer, and more particularly, a modifier which includes a compound represented by Formula 1 and is capable of improving the mixing properties between a conjugated diene-based polymer and a filler, a modified and conjugated diene-based polymer which is modified using the same, and a rubber composition including the modified and conjugated diene-based polymer.

A conjugated diene copolymer has a covalent bond reversibly dissociated and added by heat, and has at least two peaks in each of curves of molecular weight distributions measured at 40° C. and 60° C. by gel permeation chromatography, wherein a change rate of the proportion of the area of the peak having the lowest molecular weight in measurement at 60° C. to the proportion of the area of the peak having the lowest molecular weight in measurement at 40° C.

A conjugated diene copolymer has a covalent bond reversibly dissociated and added by heat, and has at least two peaks in each of curves of molecular weight distributions measured at 40° C. and 60° C. by gel permeation chromatography, wherein a change rate of the proportion of the area of the peak having the lowest molecular weight in measurement at 60° C. to the proportion of the area of the peak having the lowest molecular weight in measurement at 40° C.

The present invention is directed to a method of making a functionalized elastomer, comprising the step of polymerizing a conjugated diene monomer in the presence of a lanthanide-based coordination polymerization catalyst activated with a functionalized aluminum reagent of formula 1 ##STR00001##
where R is a linear or branched alkane group containing 1 to 8 carbon atoms, and R.sup.1 is phenylene, or a linear or branched alkane diyl group containing 2 to 10 carbon atoms, or a combination of one or more phenylene groups and one or more linear or branched alkane diyl groups containing 1 to 10 carbon atoms; Q is of formula 2 ##STR00002##
where R.sup.5, R.sup.6 and R.sup.7 are independently a linear or branched alkyl group containing 1 to 3 carbon atoms or a group of formula 3 ##STR00003##
where R3 and R4 are independently phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or R3 and R4 taken together with the nitrogen atom represent a nitrogen containing heterocyclic group containing from 4 to 12 carbon atoms; or R.sup.5, R.sup.6 and R.sup.7 taken together with the silicon atom represent a structure of formula 4 ##STR00004##
where R.sup.8 is C1 to C4 linear or branched alkanediyl and Z is N or a group of formula 5 ##STR00005##
wherein R.sup.13 is C1 to C8 alkyl.

The present invention is directed to a method of making a functionalized elastomer, comprising the step of polymerizing a conjugated diene monomer in the presence of a lanthanide-based coordination polymerization catalyst activated with a functionalized aluminum reagent of formula 1 ##STR00001##
where R is a linear or branched alkane group containing 1 to 8 carbon atoms, and R.sup.1 is phenylene, or a linear or branched alkane diyl group containing 2 to 10 carbon atoms, or a combination of one or more phenylene groups and one or more linear or branched alkane diyl groups containing 1 to 10 carbon atoms; Q is of formula 2 ##STR00002##
where R.sup.5, R.sup.6 and R.sup.7 are independently a linear or branched alkyl group containing 1 to 3 carbon atoms or a group of formula 3 ##STR00003##
where R3 and R4 are independently phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or R3 and R4 taken together with the nitrogen atom represent a nitrogen containing heterocyclic group containing from 4 to 12 carbon atoms; or R.sup.5, R.sup.6 and R.sup.7 taken together with the silicon atom represent a structure of formula 4 ##STR00004##
where R.sup.8 is C1 to C4 linear or branched alkanediyl and Z is N or a group of formula 5 ##STR00005##
wherein R.sup.13 is C1 to C8 alkyl.

The present invention is directed to a method of making a functionalized elastomer, comprising the step of polymerizing a conjugated diene monomer in the presence of a lanthanide-based coordination polymerization catalyst activated with a functionalized aluminum reagent of formula 1 ##STR00001##
where R is a linear or branched alkane group containing 1 to 8 carbon atoms, and R.sup.1 is phenylene, or a linear or branched alkane diyl group containing 2 to 10 carbon atoms, or a combination of one or more phenylene groups and one or more linear or branched alkane diyl groups containing 1 to 10 carbon atoms; Q is of formula 2 ##STR00002##
where R.sup.5, R.sup.6 and R.sup.7 are independently a linear or branched alkyl group containing 1 to 3 carbon atoms or a group of formula 3 ##STR00003##
where R3 and R4 are independently phenyl or a linear or branched alkyl group containing 1 to 10 carbon atoms, or R3 and R4 taken together with the nitrogen atom represent a nitrogen containing heterocyclic group containing from 4 to 12 carbon atoms; or R.sup.5, R.sup.6 and R.sup.7 taken together with the silicon atom represent a structure of formula 4 ##STR00004##
where R.sup.8 is C1 to C4 linear or branched alkanediyl and Z is N or a group of formula 5 ##STR00005##
wherein R.sup.13 is C1 to C8 alkyl.

A bimetallic catalytic system consists of the metallic components of formulae RLi and Ca(AR′.sub.y).sub.2(L).sub.x in which: R represents a substituted or unsubstituted C.sub.1-C.sub.10 aliphatic radical, a substituted or unsubstituted C.sub.6-C.sub.20 aromatic radical or a substituted or unsubstituted C.sub.1-C.sub.10 heteroaliphatic radical; A denotes N or C; y has the value 2 when A is N and the value 3 when A is C; each R′ represents a hydrogen atom, a substituted or unsubstituted C.sub.5-C.sub.10 aliphatic radical, a substituted or unsubstituted C.sub.6-C.sub.20 aromatic radical, a substituted or unsubstituted silyl radical, a C.sub.1-C.sub.10 aliphatic radical substituted by at least one substituted or unsubstituted silyl radical, a C.sub.6-C.sub.20 aromatic radical substituted by at least one substituted or unsubstituted silyl radical; L represents a ligand; and x is a number ranging from 0 to 4.

A modified conjugated diene-based polymer, and more particularly, a modified conjugated diene-based polymer having a unimodal molecular weight distribution curve measured by gel permeation chromatography (GPC), molecular weight distribution (PDI; MWD) of less than 1.7, and a Si content of 100 ppm or more based on weight, and a rubber composition including the same.