Methods for forming stereospecific, polar functionalized polypropylene
Methods for forming polar-functionalized isotactic and syndiotactic polypropylenes are provided, including amino-functionalized polypropylene. In embodiments, such a method comprises contacting a propylene monomer and a polar monomer comprising an amine group in the presence of an organozirconium catalyst and in the absence of a masking reagent, under conditions to induce a polymerization reaction between the propylene and polar monomers, thereby forming polar-functionalized polypropylene.
1. A method for forming polar-functionalized polypropylene, the method comprising contacting a propylene monomer and a polar monomer comprising an amine group in the presence of an organozirconium catalyst and in the absence of AlBu i 3 and/or in the absence of methylaluminoxane, under conditions to induce a polymerization reaction between the propylene and polar monomers, thereby forming polar-functionalized polypropylene.
2. The method of claim 1 , wherein the amine group has formula NR 2 , wherein each R is an independently selected unsubstituted linear alkyl group or an unsubstituted branched alkyl group.
3. The method of claim 2 , wherein each R is an independently selected unsubstituted linear alkyl group.
4. The method of claim 3 , wherein the amine group has formula N(CH 2 CH 2 CH 3 ) 2 .
5. The method of claim 1 , wherein the amine group is covalently bound via a linear alkyl group having no more than 7 carbon atoms.
6. The method of claim 1 , wherein the polar monomer has formula H 2 C═CH(CH 2 ) n NR 2 , wherein each R is an independently selected unsubstituted linear alkyl group or an unsubstituted branched alkyl group and n is an integer from 1 to 11.
7. The method of claim 6 , wherein each R is an independently selected unsubstituted linear alkyl group.
8. The method of claim 7 , wherein the polar monomer has formula H 2 C═CH(CH 2 ) n N(CH 2 CH 2 CH 3 ) 2 .
9. The method of claim 8 , wherein n is from 1 to 7.
10. The method of claim 1 , wherein the organozirconium catalyst is SBIZrMe 2 or FluZrMe 2 .
11. The method of claim 10 , wherein the polar monomer has formula H 2 C═CH(CH 2 ) n N(CH 2 CH 2 CH 3 ) 2 .
12. The method of claim 11 , wherein n is from 1 to 7.
13. The method of claim 7 , wherein the polar-functionalized polypropylene exhibits a pentad isotacticity mmmm of at least 75% or a pentad syndiotacticity rrrr of at least 70%.
14. A method for forming polar-functionalized polypropylene, the method comprising contacting a propylene monomer and a polar monomer comprising an amine group in the presence of an organozirconium catalyst, under conditions to induce a polymerization reaction between the propylene and polar monomers, thereby forming polar-functionalized polypropylene, wherein the polar-functionalized polypropylene is syndiotactic.
15. The method of claim 14 , wherein the polar-functionalized polypropylene exhibits a pentad syndiotacticity rrrr of at least 70%.
16. The method of claim 15 , wherein the organozirconium catalyst is FluZrMe 2 and the polar monomer has formula H 2 C═CH(CH 2 ) n NR 2 , wherein each R is an independently selected unsubstituted linear alkyl group and n is an integer from 1 to 11.
17. The method of claim 16 , wherein the polar monomer has formula H 2 C═CH(CH 2 ) n N(CH 2 CH 2 CH 3 ) 2 and n is from 1 to 7.
18. The method of claim 1 , wherein the contacting step is further conducted in the absence of any masking reagent capable of binding to the amine group of the polar monomer.
19. The method of claim 14 , wherein the contacting step is conducted in the absence of AlBu i 3 and in the absence of methylaluminoxane.
20. The method of claim 19 , wherein the contacting step is further conducted in the absence of any masking reagent capable of binding to the amine group of the polar monomer.
21. The method of claim 1 , wherein the organozirconium catalyst is SBIZrMe 2 and the polar monomer has formula H 2 C═CH(CH 2 ) 6 N(CH 2 CH 2 CH 3 ) 2 .