Catalysts and methods of polymerizing
View Patent ↗Provided herein are catalysts for polymerization of alkenes to cyclic poly(alkenes), and methods of making and using the same.
1. A catalyst having a structure represented by formula (I), formula (II), or formula (III):
wherein
M is a transition metal;
A is selected from the group consisting of NH 3 , N(R 3 ) 3 , Ar 1 , C 1-6 hydroxyalkyl, R 3 OR 3 , P(R 3 ) 3 , R 3 CHO, R 3 COR 3 , R 3 COOR 3 , and S(R 3 ) 2 ,
each R 3 is independently C 1 -C 22 alkyl, C 5 -C 8 cycloalkyl, Ar 1 , or two R 3 , together with the atoms to which they are attached, form a five- to eight-membered heterocycle;
L is a ketene;
E is NR 4 or S, wherein R 4 is C 1 -C 22 alkyl, C 5 -C 8 cycloalkyl, Ar 1 ;
Z-Z-Z comprises a tridentate ligand having a structure of
when the catalyst has a structure of formula (I),
when the catalyst has a structure of formula (II),
or
when the catalyst has a structure of formula (III);
each X 1 is independently O, NR 5 , or S, and R 5 is C 1 -C 22 alkyl, C 5 -C 8 cycloalkyl, or Ar 1 ;
X 2 is O, NR 6 , or S, and R 6 is C 1 -C 22 alkyl, C 5 -C 8 cycloalkyl, or Ar 1 ;
each R 1 is independently selected from H, C 1 -C 22 alkyl, C 5 -C 8 cycloalkyl, carboxyl, ester, amino, thiol, halo, C 1 -C 22 haloalkyl, and OH, or two adjacent R 1 , together with the carbon atoms to which they are attached, can form a five- to eight-membered cyclic group;
each R 2 is independently selected from H, Ar 1 , C 1 -C 22 alkyl, C 5 -C 8 cycloalkyl, halo, C 1 -C 22 haloalkyl, —NH 2 , —N—(C 1 -C 22 alkyl) 2 , —NH(C 1 -C 22 alkyl), —NHAr 1 , —NAr 1 2 , —O—Ar 1 , —O—(C 1 -C 22 alkyl), and (R 2 ) 3 —Si—;
X 3 is selected from Ar 1 , C 1 -C 22 alkyl, C 5 -C 8 cycloalkyl, C 1 -C 22 haloalkyl, and H; and
each Ar 1 is independently selected from C 6 -C 22 aryl or a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S;
with the proviso that in Formula (I), when E is S, then X 2 is not O or S.
2. The catalyst of claim 1 , wherein M comprises a group 6 transition metal.
3. The catalyst of claim 1 , wherein the catalyst has the structure of formula (I) and Z-Z-Z is
or wherein the catalyst has the structure of formula (II) and Z-Z-Z is
4. The catalyst of claim 1 , wherein the catalyst has the structure of formula (III) and Z-Z-Z is
5. The catalyst of claim 1 , wherein A is N(R 3 ) 3 , P(R 3 ) 3 , Ar 1 , S(R 3 ) 2 or R 3 OR 3 .
6. The catalyst of claim 1 , having a structure:
7. The catalyst of claim 1 , wherein at least one X 1 comprises O.
8. The catalyst of claim 1 , wherein each R 1 comprises H.
9. The catalyst of claim 1 , wherein at least one R 1 comprises a C 1 -C 6 alkyl.
10. The catalyst of claim 1 , wherein at least one R 2 comprises H, methyl, ethyl, propyl, butyl, pentyl, hexyl, naphthyl, cyclohexyl, C 1 -C 22 haloalkyl, or C 6 -C 22 aryl.
11. The catalyst of claim 1 , wherein X 3 comprises H, methyl, ethyl, propyl, butyl, pentyl, hexyl, naphthyl, cyclohexyl, or C 6 -C 22 aryl.
12. The catalyst of claim 1 , selected from the group consisting of
13. A method for making the catalyst of claim 1 , comprising
reacting a complex of formula (IV) or formula (VI) and CS 2 or an isocyanate having a structure of formula (V) under conditions sufficient to form the catalyst:
wherein
each L is independently absent or selected from phosphine, phosphite, phosphonite, phosphinite, amine, amide, imine, alkoxy, ether, thioether, and a five- or six-membered monocyclic group having 1 to 3 ring heteroatoms;
or both L together comprise a bidentate ligand.
14. The method of claim 13 , wherein the complex of formula (IV) has a structure represented by a formula:
15. The method of claim 13 , wherein the complex of formula (VI) has a structure represented by a formula:
16. The method of claim 13 , wherein at least one L is absent, phosphine, amine, ether, or a five- or six-membered monocyclic group having 1 to 3 heteroatoms.
17. The method of claim 13 , wherein both L together comprise a bidentate ligand.
18. A method of preparing a cyclic polymer, comprising:
admixing a plurality of alkenes in the presence of the catalyst of formula (I) or formula (II) of claim 1 under conditions sufficient to polymerize the plurality of alkenes, thereby forming the cyclic polymer, wherein the cyclic polymer ring comprises alkene groups.
19. The method of claim 18 , wherein the plurality of alkenes are cyclic alkenes comprising unsubstituted or substituted cyclopropene, cyclobutene, cyclopentene, cycloheptene, cyclooctene, norbornene, dicyclopentadiene, norbornene anhydride, diester from norbornene anhydride, imide from norbornene anhydride, oxanorbornene, oxanorbornene anhydride, ester of oxanorbornene anhydride, and imide of oxanorbornene anhydride, or combinations thereof, wherein the ester is from a C 1 -C 10 alkyl or aryl alcohol, the imide is from C 1 -C 10 alkyl or aryl amine; wherein substituents are C 1 -C 10 alkyl, aryl, C 1 -C 10 alkoxy, aryloxy, C 1 -C 10 carboxylic acid ester, or carboxylic acid amide, optionally substituted one or two times with C 1 -C 10 alkyl or aryl.
20. The method of claim 18 , further comprising hydrogenating the cyclic polymer alkene groups to form cyclic polymer alkane groups.