Polymerisation initiators

1. A method of making a polymer, comprising the step of reacting

i) a polymerization initiator, represented by the following Formula 1 ,

or a Lewis base adduct thereof, and

ii) at least one type of polymerizable monomers selected from conjugated olefins and aromatic vinyl compounds,

wherein

each M 1 is independently selected from lithium, sodium and potassium;

each R 1 is independently selected from (C 1 -C 100 ) alkyl and (C 2 -C 100 ) alkenyl, optionally substituted with one or more (C 6 -C 12 ) aryl groups and optionally linked to the carbon atom C by up to 25 monomer units selected from conjugated diene monomers and aromatic vinyl compounds, especially butadiene, isoprene and styrene;

each R 12 is independently selected from hydrogen, (C 1 -C 10 ) alkyl, (C 6 -C 12 ) aryl and (C 7 -C 18 ) alkylaryl;

each Y 1 is independently selected from a nitrogen atom, a sulfur atom and a silicon atom;

R 3 , R 4 and R 5 are each independently selected from (C 1 -C 18 ) alkyl, di(C 1 -C 6 ) alkyl amine (only when Y 1 is a silicon atom), (C 6 -C 18 ) aryl, (C 7 -C 18 ) alkylaryl and, when Y 1 is not a silicon atom, —SiR 14 R 15 R 16 , wherein R 14 , R 15 and R 16 are each independently selected from (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl and (C 7 -C 18 ) alkylaryl; n and o are each an integer selected from 0 and n+o=1 when Y 1 =N, n=o=0 when Y 1 =S, and n+o=2 when Y 1 =Si;

m is an integer selected from 1, 2 and 3;

each E is independently selected from (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl, (C 7 -C 18 ) alkylaryl and —Y 3 (R 9 )(R 10 ) t (R 11 ) u , wherein

Y 3 is selected from a nitrogen atom, a sulfur atom and a silicon atom; R 9 , R 10 and R 11 are each independently selected from (C 1 -C 18 ) alkyl, di(C 1 -C 6 ) alkyl amine (only when Y 3 is a silicon atom), (C 6 -C 18 ) aryl, (C 7 -C 18 ) alkylaryl, and, when Y 3 is not a silicon atom, —SiR 20 R 21 R 22 , wherein R 20 , R 21 and R 22 are each independently selected from (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl and (C 7 -C 18 ) alkylaryl; t and u are each an integer selected from 0 and 1; and t+u=1 when Y 3 =N, t=u=0 when Y 3 =S, and t+u=2 when Y 3 =Si;

s is an integer selected from 0, 1 and 2;

each F is independently selected from (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl, (C 7 -C 18 ) alkylaryl and —Y 2 (R 6 )(R 7 ) q (R 8 ) r , wherein

Y 2 is selected from a nitrogen atom, a sulfur atom and a silicon atom; R 6 , R 7 and R 8 are each independently selected from (C 1 -C 18 ) alkyl, di(C 1 -C 6 ) alkyl amine (only when Y 2 is a silicon atom), (C 6 -C 18 ) aryl, (C 7 -C 18 ) alkylaryl and, when Y 2 is not a silicon atom, —SiR 17 R 18 R 19 , wherein R 17 , R 18 and R 19 are each independently selected from (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl and (C 7 -C 18 ) alkylaryl; q and r are each an integer selected from 0 and 1; and q+r=1 when Y 2 =N, q=r=0 when Y 2 =S, and q+r=2 when Y 2 =Si;

p is an integer selected from 0, 1, 2 and 3;

K is selected from nitrogen, >C-H and >C-H and >C-Y 3 (R 9 )(R 10 ) t (R 11 ) u , wherein Y 3 ,R 9 ,R 10 , R 11 , t and u are independently as defined above.

2. The method according to claim 1 , wherein the at least one type of polymerizable monomers is selected from 1,3-butadiene, isoprene and styrene.

3. The method according to claim 1 , further comprising a step of reacting the polymer with one or more chain end modifying agents so as to provide a chain end-modified polymer.

4. The method according to claim 3 , wherein the one or more chain end modifying agents are represented by the following Formulas 8, 9, 10, 11, 12, 13, 14, 15 and 16 and Lewis base adducts thereof:

wherein M 3 is a silicon atom or a tin atom;

T is at least divalent and is selected from (C 6 -C 18 ) aryl, (C 7 -C 18 ) alkylaryl and (C 1 -C 18 ) alkyl, wherein each group is optionally substituted with one or more groups selected from di(C 1 -C 7 hydrocarbyl)amino, bis(tri(C 1 -C 12 alkyl)silyl)amino, tris(C 1 -C 7 hydrocarbyl)silyl, (C 7 -C 18 ) alkylaryl and (C 6 -C 18 ) aryl;

R 23 and R 26 are each independently selected from (C 1 -C 4 ) alkyl;

R 24 , R 25 , R 27 and R 28 are each independently selected from (C 1 -C 18 ) alkyl, (C 6 -C 18 ) aryl and (C 7 -C 18 ) alkylaryl;

a and c are each independently selected from 0, 1 and 2; b and d are each independently selected from 1, 2 and 3; a+b=3; and c+d=3;

wherein M 4 is a silicon atom or a tin atom;

U is at least divalent and is selected from (C 6 -C 18 ) aryl, (C 7 -C 18 ) alkylaryl and (C 1 -C 18 ) alkyl, wherein each group is optionally substituted with one or more groups selected from di(C 1 -C 7 hydrocarbyl)amino, bis(tri(C 1 -C 12 alkyl)silyl)amino, tris(C 1 -C 7 hydrocarbyl)silyl, (C 7 -C 18 ) alkylaryl and (C 6 -C 18 ) aryl;

R 29 is independently selected from (C 1 -C 4 ) alkyl, (C 6 -C 18 ) aryl and (C 7 -C 18 ) alkylaryl;

R 31 , R 32 and R 33 are each independently selected from (C 1 -C 18 ) alkyl, (C 1 -C 18 ) alkoxy, (C 6 -C 18 ) aryl and (C 7 -C 18 ) alkylaryl;

R 30 is independently selected from (C 1 -C 18 ) alkyl, (C 1 -C 18 ) alkoxy, (C 6 -C 18 ) aryl, (C 7 -C 18 ) alkylaryl and R 34 —(C 2 H 4 O) g —O—, wherein R 34 is selected from (C 5 -C 23 ) alkyl, (C 5 -C 23 ) alkoxy, (C 6 -C 18 ) aryl and (C 7 -C 25 ) alkylaryl and g is selected from 4, 5 and 6;

e is selected from 0, 1 and 2; f is selected from 1, 2 and 3; and e+f=3;

wherein V is at least divalent and is selected from (C 6 -C 18 ) aryl, (C 7 -C 18 ) alkylaryl and (C 1 -C 18 ) alkyl, wherein each group is optionally substituted with one or more groups selected from di(C 1 -C 7 hydrocarbyl)amino, bis(tri(C 1 -C 12 alkyl)silyl)amino, tris(C 1 -C 7 hydrocarbyl)silyl, (C 7 -C 18 ) alkylaryl and (C 6 -C 18 ) aryl;

R 35 is independently selected from (C 1 -C 4 ) alkyl, (C 6 -C 18 ) aryl and (C 7 -C 18 ) alkylaryl;

R 37 , R 38 , R 39 , R 40 , R 41 and R 42 are each independently selected from (C 1 -C 18 ) alkyl, (C 1 -C 18 ) alkoxy, (C 6 -C 18 ) aryl and (C 7 -C 18 ) alkylaryl;

R 36 is independently selected from (C 1 -C 18 ) alkyl, (C 1 -C 18 ) alkoxy, (C 6 -C 18 ) aryl, (C 7 -C 18 ) alkylaryl and R 43 —(C 2 H 4 O) j —O—, wherein R 43 is selected from (C 5 -C 23 ) alkyl, (C 5 -C 23 ) alkoxy, (C 6 -C 18 ) aryl and (C 7 -C 25 ) alkylaryl; and j is selected from the 4, 5 and 6;

i is selected from 0, 1 and 2; h is selected from 1, 2 and 3; and i+h=3;

wherein R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 51 , R 52 , R 53 and R 54 are each independently selected from hydrogen, (C 1 -C 16 ) alkyl, (C 6 -C 16 ) aryl and (C 7 -C 16 ) alkylaryl; and

R 50 is at least divalent and is selected from (C 6 -C 18 ) aryl, (C 7 -C 18 ) alkylaryl and (C 1 -C 18 ) alkyl, wherein each group is optionally substituted with one or more groups selected from di(C 1 -C 7 hydrocarbyl)amino, bis(tri(C 1 -C 12 alkyl)silyl)amino, tris(C 1 -C 7 hydrocarbyl)silyl, (C 7 -C 18 ) alkylaryl and (C 6 -C 18 ) aryl;

wherein R 55 , R 56 , R 57 , R 58 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 , R 68 , R 69 , R 70 and R 71 are each independently selected from hydrogen, (C 1 -C 16 ) alkyl, (C 6 -C 16 ) aryl and (C 7 -C 16 ) alkylaryl;

R 59 is selected from (C 1 -C 4 ) alkyl, (C 6 -C 18 ) aryl and (C 7 -C 18 ) alkylaryl;

W is at least divalent and is selected from (C 6 -C 18 ) aryl, (C 7 -C 18 ) alkylaryl and (C 1 -C 18 ) alkyl, wherein each group is optionally substituted with one or more groups selected from di(C 1 -C 7 hydrocarbyl)amino, bis(tri(C 1 -C 12 alkyl)silyl)amino, tris(C 1 -C 7 hydrocarbyl)silyl, (C 7 -C 18 ) alkylaryl and (C 6 -C 18 ) aryl;

k is selected from 0, 1 and 2; 1 is selected from 1, 2 and 3; k+1=3; and v is selected from 1 to 20; and

F 1 and F 2 are independently selected from hydrogen, hydroxy, chlorine, bromine, iodine, —SiR 52 R 53 R 54 , wherein R 52 , R 53 , and R 54 are the same or different and are as defined for Formulas 12 and 13, vinyl, (C 6 -C 16 ) aryl, (C 7 -C 16 ) alkylaryl and (C 1 -C 16 ) alkyl, wherein each hydrocarbyl group is optionally substituted with one or more groups selected from hydroxyl, di(C 1 -C 7 hydrocarbyl)amino, bis(tri(C 1 -C 12 alkyl)silyl)amino and an epoxy group.

5. A polymer obtainable by the method as defined in claim 1 .

6. A polymer composition comprising the polymer or chain end-modified polymer as defined in claim 5 and one or more further components selected from (i) components which are added to or formed as a result of the polymerization process used for making said polymer and (ii) components which remain after solvent removal from the polymerization process.

7. The polymer composition according to claim 6 , comprising one or more components selected from extender oils, stabilizers and further polymers.

8. The polymer composition as defined in claim 6 , further comprising one or more fillers.

9. The polymer composition as defined in claim 8 , wherein the one or more fillers are selected from carbon black, carbon nanotubes, graphite, graphene, silica, carbon-silica dual-phase filler, clays, calcium carbonate, magnesium carbonate, lignin, glass particle-based fillers, and starch-based fillers.

10. The polymer composition as defined in claim 6 , further comprising one or more vulcanizing agents.

11. A vulcanized polymer composition which is obtained by vulcanizing the polymer composition as defined in claim 10 .

12. A method of making a vulcanized polymer composition, comprising the step of vulcanizing the polymer composition as defined in claim 10 .

13. An article comprising at least one component formed from the vulcanized polymer composition as defined in claim 11 .

14. The method of making a polymer according to claim 1 wherein the polymerization initiator is represented by the following Formula 5:

or a Lewis base adduct thereof,

wherein

M 1 is lithium;

each R 1 is independently selected from (C 1 -C 18 ) alkyl;

p is an an integer selected from 1, 2 and 3;

K is selected from nitrogen and >C—H; and

all other substituents or groups are as defined for Formula 1 in claim 1 .

15. The method of making a polymer according to claim 14 ,

wherein

each R 1 is independently selected from (C 1 -C 7 ) alkyl;

R 12 is hydrogen;

R 3 , R 4 and R 5 are each independently selected from (C 1 -C 10 ) alkyl and, when Y 1 is not a silicon atom, —SiR 14 R 15 R 16 , wherein R 14 , R 15 and R 16 are each independently selected from (C 1 -C 16 ) alkyl; and

R 6 , R 7 and R 8 are each independently selected from (C 1 -C 10 ) alkyl and, when Y 2 is not a silicon atom, —SiR 17 R 18 R 19 , wherein R 17 , R 18 and R 19 are each independently selected from (C 1 -C 16 ) alkyl.

16. The method of making a polymer according to claim 14 ,

wherein

each R 1 is independently selected from (C 1 -C 10 ) alkyl;

R 12 is hydrogen;

R 3 , R 4 and R 5 are each independently selected from (C 1 -C 18 ) alkyl and, when Y 1 is not a silicon atom, —SiR 14 R 15 R 16 , wherein R 14 , R 15 and R 16 are each independently selected from (C 1 -C 10 ) alkyl;

R 6 , R 7 and R 8 are each independently selected from (C 1 -C 18 ) alkyl and, when Y 2 is not a silicon atom, —SiR 17 R 18 and R 19 , wherein R 17 , R 18 and R 19 are each independently selected from (C 1 -C 10 ) alkyl;

m and p are each independently selected from an integer of 1 and 2.

17. The method of making a polymer according to claim 1 , wherein the polymerization initiator is represented by the following Formula 6:

or a Lewis base adduct thereof,

wherein

M 1 is lithium;

each R 1 is independently selected from (C 1 -C 10 ) alkyl;

R 12 is hydrogen;

R 3 , R 4 and R 5 are each independently selected from (C 1 -C 18 ) alkyl and, when Y 1 is not a silicon atom, —SiR 14 R 15 R 16 , wherein R 14 , R 5 and R 16 are each independently selected from (C 1 -C 10 ) alkyl;

m and p are each independently an integer selected from 1 and 2;

R 6 , R 7 and R 8 are each independently selected from (C 1 -C 18 ) alkyl and, when Y 2 is not a silicon atom, —SiR 17 R 18 R 19 , wherein R 17 , R 18 and R 19 are each independently selected from (C 1 -C 10 ) alkyl; and

all other substituents or groups are as defined for Formula 1 in claim 1 .

18. The method of making a polymer according to claim 17 ,

wherein

each R 1 is independently selected from (C 1 -C 7 ) alkyl;

R 12 is hydrogen;

R 3 , R 4 and R 5 are each independently selected from (C 1 -C 10 ) alkyl and, when Y 1 is not a silicon atom, —SiR 14 R 15 R 16 , wherein R 14 , R 15 and R 16 are selected from (C 1 -C 10 ) alkyl; and

R 6 , R 7 and R 8 are each independently selected from (C 1 -C 10 ) alkyl and, when Y 2 is not a silicon atom, —SiR l7 R 18 R 19 , wherein R 17 , R 18 and R 19 are each independently selected from (C 1 -C 10 ) alkyl.

19. The method of making a polymer according to claim 1 , wherein the polymerization initiator is represented by the following Formula 17, 18 or 19:

or Lewis base adducts thereof,

wherein

M 1 is lithium;

each R 1 is independently selected from (C 1 -C 18 ) alkyl; and

all other substituents or groups are as defined for Formula 1 in claim 1 .

20. The method of making a polymer according to claim 19 , wherein

each R 1 is independently selected from (C 1 -C 10 ) alkyl;

R 12 is hydrogen;

R 3 , R 4 and R 5 are each independently selected from (C 1 -C 18 ) alkyl and, when Y 1 is not a silicon atom, —SiR 14 R 15 R 16 ; wherein R 14 , R 15 and R 16 are selected from (C 1 -C 10 ) alkyl; and

R 6 , R 7 and R 8 are each independently selected from (C 1 -C 18 ) alkyl and, when Y 2 is not a silicon atom, —SiR 17 R 18 R 19 , wherein R 17 , R 18 and R 19 are each independently selected from (C 1 -C 10 ) alkyl.

21. The method of making a polymer according to claim 19 , wherein

each R 1 is each independently selected from (C 1 -C 7 ) alkyl;

R 12 is hydrogen;

R 3 , R 4 and R 5 are each independently selected from (C 1 -C 10 ) alkyl and, when Y 1 is not a silicon atom, —SiR 14 R 15 R 16 ; wherein R 14 , R 15 and R 16 are selected from (C 1 -C 10 ) alkyl; and

R 6 , R 7 and R 8 are each independently selected from (C 1 -C 18 ) alkyl and, when Y 2 is not a silicon atom, —SiR 17 R 18 R 19 , wherein R 17 , R 18 and R 19 are each independently selected from (C 1 -C 10 ) alkyl.