Dual- or multi-headed chain shuttling agents and their use for preparation of block copolymers

1. A chain shuttling agent having the formula:

R 1 [M A -R 2 —] N M A R 1 ,

R 1 [M B R 1 —R 2 —] N M B (R 1 ) 2 ,

M C [R 2 ] 2 M C , or

M B [R 2 ] 3 M B ;

or an aggregate thereof, a Lewis base-containing derivative thereof, or any combination thereof; wherein

M A is Zn or Mg;

M B is B, or Ga;

M C is Mg;

R 1 in each occurrence is independently selected from hydrogen, halide, amide, hydrocarbyl, hydrocarbylamide, dihydrocarbylamide, hydrocarbyloxide, hydrocarbylsulfide, dihydrocarbylphosphido, tri(hydrocarbyl)silyl; any hydrocarbyl group being optionally substituted with at least one halide, amide, hydrocarbylamide, dihydrocarbylamide, or hydrocarbyloxide; and each carbon-containing R 1 having from 1 to 20 carbon atoms, inclusive;

R 2 in each occurrence is independently selected from (CH 2 ) m , O[(CH 2 ) n CH 2 CH 2 ] 2 , S[(CH 2 ) n CH 2 CH 2 ] 2 , R A N[(CH 2 ) n CH 2 CH 2 ] 2 , (R B ) 2 Si[(CH 2 ) n CH 2 CH 2 ] 2 , (R B ) 3 SiOSiR B [(CH 2 ) n CH 2 CH 2 ] 2 , or [Si(R B ) 2 (CH 2 ) n CH 2 CH 2 ] 2 O; wherein n in each occurrence is independently an integer from 1 to 20, inclusive; m is an integer from 2 to 20, inclusive; R A is H or a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and R B in each occurrence is independently a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and

N, on average, in each occurrence is a number from 2 to 150, inclusive.

2. A process for the polymerization of at least one addition polymerizable monomer to form a polymer composition, the process comprising:

contacting at least one addition polymerizable monomer with a catalyst composition under polymerization conditions; wherein

the catalyst composition comprises the contact product of at least one polymerization catalyst precursor, at least one cocatalyst, and the chain shuttling agent of claim 1 .

3. A multiblock copolymer obtained by a process comprising:

contacting at least one addition polymerizable monomer with a catalyst composition under polymerization conditions; wherein

the catalyst composition comprises the contact product of at least one polymerization catalyst precursor, at least one cocatalyst, and a chain shuttling agent having the formula:

R 1 [M A -R 2 —] N M A R 1 ,

R 1 [M B R 1 —R 2 —] N M B (R 1 ) 2 ,

M C [R 2 ] 2 M C , or

M B [R 2 ] 3 M B ;

or an aggregate thereof, a Lewis base-containing derivative thereof, or any combination thereof; wherein

M A is Zn or Mg;

M B is B, Al, or Ga;

M C is Mg;

R 1 in each occurrence is independently selected from hydrogen, halide, amide, hydrocarbyl, hydrocarbylamide, dihydrocarbylamide, hydrocarbyloxide, hydrocarbylsulfide, dihydrocarbylphosphido, tri(hydrocarbyl)silyl; any hydrocarbyl group being optionally substituted with at least one halide, amide, hydrocarbylamide, dihydrocarbylamide, or hydrocarbyloxide; and each carbon-containing R 1 having from 1 to 20 carbon atoms, inclusive;

R 2 in each occurrence is independently selected from (CH 2 ) m , O[(CH 2 ) n CH 2 CH 2 ] 2 , S[(CH 2 ) n CH 2 CH 2 ] 2 , R A N[(CH 2 ) n CH 2 CH 2 ] 2 , (R B ) 2 Si[(CH 2 ) n CH 2 CH 2 ] 2 , (R B ) 3 SiOSiR B [(CH 2 ) n CH 2 CH 2 ] 2 , or [Si(R B ) 2 (CH 2 ) n CH 2 CH 2 ] 2 O; wherein n in each occurrence is independently an integer from 1 to 20, inclusive; m is an integer from 2 to 20, inclusive; R A is H or a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and R B in each occurrence is independently a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and

N, on average, in each occurrence is a number from 2 to 150, inclusive.

4. A catalyst composition comprising the contact product at least one polymerization catalyst precursor, at least one cocatalyst, and a chain shuttling agent having the formula:

R 1 [M A -R 2 —] N M A R 1 ,

R 1 [M B R 1—R 2 —] N M B (R 1 ) 2 ,

M C [R 2 ] 2 M C , or

M B [R 2 ] 3 M B ;

or an aggregate thereof, a Lewis base-containing derivative thereof, or any combination thereof; wherein

M A is Zn or Mg;

M B is B, Al, or Ga;

M C is Mg;

R 1 in each occurrence is independently selected from hydrogen, halide, amide, hydrocarbyl, hydrocarbylamide, dihydrocarbylamide, hydrocarbyloxide, hydrocarbylsulfide, dihydrocarbylphosphido, tri(hydrocarbyl)silyl; any hydrocarbyl group being optionally substituted with at least one halide, amide, hydrocarbylamide, dihydrocarbylamide, or hydrocarbyloxide; and each carbon-containing R 1 having from 1 to 20 carbon atoms, inclusive;

R 2 in each occurrence is independently selected from (CH 2 ) m , O[(CH 2 ) n CH 2 CH 2 CH 2 ] 2 , S[(CH 2 ) n CH 2 CH 2 ] 2 ,R A N[(CH 2 ) n CH 2 CH 2 ] 2 , (R B ) 2 Si[(CH 2 ) n CH 2 CH 2 ] 2 , (R B ) 3 SiOSiR B [(CH 2 ) n CH 2 CH 2 ] 2 , or [Si(R B ) 2 (CH 2 ) n CH 2 CH 2 ] 2 O; wherein n in each occurrence is independently an integer from 1 to 20, inclusive; m is an integer from 2 to 20, inclusive; R A is H or a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and R B in each occurrence is independently a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and

N, on average, in each occurrence is a number from 2 to 150, inclusive.

5. A chain shuttling agent represented by the following Newkome dendrimer nomenclature:

an aggregate thereof, a Lewis base-containing derivative thereof, or any combination thereof; wherein:

C is a core selected from a metal, alkadiyl di(metal), alkatriyl tri(metal), or alkatetrayl tetra(metal), wherein the metal is Zn, Mg, B, Al, or Ga, and any carbon-containing core has from 2 to 20 carbon atoms;

R in each occurrence is a repeat unit selected from an alkadiyl metal, alkatriyl di(metal), or alkatetrayl tri(metal) having from 2 to 20 carbon atoms and a branch multiplicity of N b ;

G is the generation of the dendrimer cascade;

Z is a terminal monovalent having up to 20 carbon atoms;

N c , is the branch multiplicity of the core; and

the shuttling agent comprises at least one generation of repeat unit R, such that G on average is a number from 2 to 150, inclusive.

6. A process for the polymerization of at least one addition polymerizable monomer to form a polymer composition, the process comprising:

contacting at least one addition polymerizable monomer with a catalyst composition under polymerization conditions;

wherein the catalyst composition comprises the contact product of at least one polymerization catalyst precursor, at least one cocatalyst, and the shuttling agent of claim 5 .

7. A multiblock copolymer obtained by the process of claim 6 .

8. A catalyst composition comprising the contact product at least one polymerization catalyst precursor, at least one cocatalyst, and the shuttling agent of claim 5 .

9. A process for preparing the chain shuttling agent of claim 5 comprising:

a) providing a polyene having the formula R A C[(CH 2 ) n CH═CH 2 ] 3 or C[(CH 2 ) n CH═CH 2 ] 4 , wherein n in each occurrence is independently an integer from 0 to 20 and R A is H or a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and

b) contacting the polyene with a borohydride having the formula (R C ) 2 BH, wherein R C is a hydrocarbyl having from 1 to 20 carbon atoms, to form a first composition comprising a partially hydroborated polyene;

c) contacting the first composition with M A (R 1A ) 2 or M B (R 1A ) 3 to form a second composition, comprising M A {CH 2 CH 2 (CH 2 ) n E[(CH 2 ) n CH═CH 2 ] m−1 } 2 or

M B {CH 2 CH 2 (CH 2 ) n E[(CH 2 ) n CH═CH 2 ] m−1 } 3 wherein R 1A in each occurrence is independently a hydrocarbyl having from 1 to 20 carbon atoms, inclusive, optionally substituted with at least one halide, amide, hydrocarbylamide, dihydrocarbylamide, or hydrocarbyloxide;

d) contacting the second composition with (R C ) 2 BH, followed by contacting the resulting composition with M A (R 1A ) 2 or M B (R 1A ) 3 to form a third composition;

e) contacting the third composition with a partially hydroborated polyene prepared according to step b); and

f) repeating steps d) and e) any number of times to form a dendrimeric chain shuttling agent.

10. A process for preparing a chain shuttling agent having the formula:

R 1 [M A -R 2 —] N M A R 1 , wherein M A is Zn or Mg, or

R 1[M B R 1 —R 2—] N M B (R 1 ) 2 , wherein M B is B, Al, or Ga;

or an aggregate thereof, a Lewis base-containing derivative thereof, or any combination thereof; the process comprising:

a) providing an α,ω-diene having the formula CH 2 ═CH(CH 2 ) n CH═CH 2 , O[(CH 2 ) n CH═CH 2 ] 2 , S[(CH 2 ) n CH═CH 2 ] 2 , R A N[(CH 2 ) n CH═CH 2 ] 2 , (R B ) 2 Si[(CH 2 ) n CH═CH 2 ] 2 , (R B )3SiOSiR B [(CH 2 ) n CH═CH 2 ] 2 , or [Si(R B ) 2 (CH 2 ) n CH═CH 2 ] 2 O; wherein n in each occurrence is

independently an integer from 0 to 20, inclusive; R A is H or a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and R B in each occurrence is independently a hydrocarbyl having from 1 to 12 carbon atoms, inclusive;

b) contacting the α,ω-diene with a borohydride compound having the formula (R C ) 2 BH, wherein R C is a hydrocarbyl having from 1 to 20 carbon atoms, to form a first composition; and

c) contacting the first composition with M A (R 1A )(R 1 ) or M B (R 1A )(R 1 ) 2 to form a second composition comprising the chain shuttling agent;

wherein

R 1A in each occurrence is independently selected from hydrogen or a hydrocarbyl having from 1 to 20 carbon atoms, inclusive, optionally substituted with at least one halide, amide, hydrocarbylamide, dihydrocarbylamide, or hydrocarbyloxide;

R 1 in each occurrence is independently selected from hydrogen, halide, amide, hydrocarbyl, hydrocarbylamide, dihydrocarbylamide, hydrocarbyloxide, hydrocarbylsulfide, dihydrocarbylphosphido, tri(hydrocarbyl)silyl; any hydrocarbyl group being optionally substituted with at least one halide, amide, hydrocarbylamide, dihydrocarbylamide, or hydrocarbyloxide; and each carbon-containing R 1 having from 1 to 20 carbon atoms, inclusive;

R 2 in each occurrence is independently selected from (CH 2 ) m , O[(CH 2 ) n CH 2 CH 2 ] 2 , S[(CH 2 ) n CH 2 CH 2 ] 2 , R A N[(CH 2 ) n CH 2 CH 2 ] 2 , (R B ) 2 Si[(CH 2 ) n CH 2 CH 2 ] 2 , (R B ) 3 SiOSiR B [(CH 2 ) n CH 2 CH 2 ] 2 , or [Si(R B ) 2 (CH 2 ) n CH 2 CH 2 ] 2 O; wherein n in each occurrence is independently an integer from 1 to 20, inclusive; m is an integer from 2 to 20, inclusive; R A is H or a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and R B in each occurrence is independently a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and

N, on average, in each occurrence is a number from 2 to 150, inclusive.

11. A chain shuttling agent having the formula:

R 1 [M B R 1 —R 2 —] N M B (R 1 ) 2 , or

M B [R 2 ] 3 M B ;

or an aggregate thereof, a Lewis base-containing derivative thereof, or any combination thereof; wherein

M B is Al;

R 1 in each occurrence is independently selected from hydrogen, halide, amide, hydrocarbyl, hydrocarbylamide, dihydrocarbylamide, hydrocarbyloxide, hydrocarbylsulfide, dihydrocarbylphosphido, tri(hydrocarbyl)silyl; any hydrocarbyl group being optionally substituted with at least one halide, amide, hydrocarbylamide, dihydrocarbylamide, or hydrocarbyloxide; and each carbon-containing R 1 having from 1 to 20 carbon atoms, inclusive;

R 2 in each occurrence is independently selected from (CH 2 ) m , O[(CH 2 ) n CH 2 CH 2 ] 2 , S[(CH 2 ) n CH 2 CH 2 ] 2 , R A N[(CH 2 ) n CH 2 CH 2 ] 2 , (R B ) 2 Si[(CH 2 ) n CH 2 CH 2 ] 2 , (R B ) 3 SiOSiR B [(CH 2 ) n CH 2 CH 2 ] 2 , or [Si(R B ) 2 (CH 2 ) 2 CH 2 CH 2 ] 2 O; wherein n in each occurrence is independently an integer from 1 to 20, inclusive; m is an integer from 3 to 20, inclusive; R A is H or a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and R B in each occurrence is independently a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and

N, on average, in each occurrence is a number from 2 to 150, inclusive.