Polyfarnesenes by metal-catalyzed insertion polymerizations
View Patent ↗Provided herein are polyfarnesenes such as farnesene homopolymers derived from a farnesene and farnesene interpolymers derived from a farnesene and at least a vinyl monomer; and the processes of making and using the polyfarnesenes. The farnesene homopolymer can be prepared by polymerizing the farnesene in the presence of a catalyst such as a Ziegler-Natta catalyst, a Kaminsky catalyst, a metallocene catalyst, an organolithium reagent or a combination thereof. In some embodiments, the farnesene is prepared from a sugar by using a microorganism.
1. A method of making a polyfarnesene comprising polymerizing a farnesene in the presence of a catalyst, wherein the farnesene is α-farnesene or β-farnesene or a combination thereof, and wherein an amount of a cis-1,4-microstructure in the polyfarnesene is at most about 80 wt. %, based on a total weight of the polyfarnesene.
2. The method of claim 1 , wherein the catalyst is a Ziegler-Natta catalyst, a Kaminsky catalyst, a metallocene catalyst, an organolithium reagent or a combination thereof.
3. The method of claim 1 , wherein the catalyst is a Ziegler-Natta catalyst.
4. The method of claim 3 , wherein the Ziegler-Natta catalyst comprises (1) a transition metal compound comprising an element from groups IV to VIII of the periodic table; and (2) an organometallic compound comprising a metal from groups I to III of the periodic table.
5. The method of claim 4 , wherein the transition metal compound further comprises one or more anions and ligands.
6. The method of claim 5 , wherein the one or more anions and ligands are selected from halides, oxyhalides, alkoxy, acetylacetonyl, cyclopentadienyl and phenyl.
7. The method of claim 6 , wherein the element from groups IV to VIII is titanium, vanadium, chromium, molybdenum, zirconium, iron or cobalt.
8. The method of claim 4 , wherein the organometallic compound is a hydride, alkyl or aryl of the metal from groups I to III, wherein the metal is selected from aluminum, lithium, zinc, tin, cadmium, beryllium and magnesium.
9. The method of claim 4 , wherein the organometallic compound is an alumoxane, an alkylaluminum compound, diethylzinc, di(i-butyl)zinc, di(n-hexyl)zinc or ethylzinc (t-butoxide).
10. The method of claim 9 , wherein the alkylaluminum compound is trimethylaluminum, triethylaluminum, diethyl aluminum chloride, trimethylaluminum, triisobutylaluminum or trioctylaluminum.
11. The method of claim 1 , wherein the catalyst is a Kaminsky catalyst.
12. The method of claim 11 , wherein the Kaminsky catalyst has formula Cp 2 MX 2 or formula (XVI):
where each M is a transition metal; each X is a halogen, alkyl or a combination thereof; each R is H or alkyl; each Cp is a ferrocenyl group; and Z is a divalent bridging group selected from C(CH 3 ) 2 , Si(CH 3 ) 2 or CH 2 CH 2 .
13. The method of claim 12 , wherein the transition metal is Zr, Ti or Hf.
14. The method of claim 1 , wherein the catalyst is a metallocene catalyst.
15. The method of claim 1 , wherein the catalyst is an organolithium reagent.
16. The method of claim 15 , wherein the catalyst further comprises 1,2-bis(dimethylamino)ethane.
17. The method of claim 15 , wherein the organolithium reagent is n-butyl lithium or sec-butyl lithium.
18. The method of claim 1 further comprising a step of making the farnesene from a simple sugar by a microorganism.
19. A polyfarnesene prepared by the method of claim 1 .
20. The method of claim 1 , wherein the farnesene is copolymerized with at least one vinyl monomer and wherein the at least one vinyl monomer is ethylene, an α-olefin, a substituted or unsubstituted vinyl halide, vinyl ether, acrylonitrile, acrylic ester, methacrylic ester, acrylamide or methacrylamide or a combination thereof.
21. The method of claim 1 , wherein the farnesene is copolymerized with at least one vinyl monomer wherein the at least one vinyl monomer is ethylene or styrene.