Catalytic upcycling of polyolefins via versatile alkylaluminums

1. A process comprising:

providing one or more polymers, oligomers, or mixtures thereof;

providing a compound of formula (I):

Al(R 1 ) 3   (I),

wherein

R 1 is independently selected at each occurrence thereof from the group consisting of H, aryl, C 1 -C 8 alkyl, and C 1 -C 8 alkoxy;

contacting the polymers, oligomers, or mixtures thereof with the compound of formula (I), as a reaction mixture, in the presence of a catalyst having a formula (II):

Met(R 2 ) n @support  (II),

wherein

Met is a metal selected from the group consisting of zirconium, titanium, hafnium, scandium, yttrium, lanthanum, and lutetium;

R 2 is independently selected at each occurrence thereof from the group consisting of H, C 1 -C 10 alkyl, C 5 -C 10 alkoxy, and BH 4 ;

n is an integer ranging from 1 to 3; and

support is selected from the group consisting of silica, silica/alumina, and zeolites, under conditions effective to form alkanes, carboxylic acids, alcohols, alkyl halides, or aldehydes, which are shorter than the polymers, the oligomers, or the mixtures thereof; and

recovering the formed shorter alkanes, carboxylic acids, alcohols, alkyl halides, or aldehydes.

2. The process of claim 1 , wherein the catalyst of formula (II) is selected from the group consisting of Zr(CH 2 CMe 3 ) n @SiAlO x , Zr(OCH 2 CMe 3 ) n @SiAlO x , Zr(CH 2 CMe 3 ) n @SiO 2 , Zr(H) n @SiO 2 , and Zr(H) n @SiAlO x , wherein n is an integer ranging from 1-3.

3. The process of claim 1 , wherein the compound of formula (I) is selected from the group consisting of AliBu 3 , AlEt 3 , AlMe 3 , AlPh 3 , Al(C 8 H 17 ) 3 , and AlH 3 .

4. The process of claim 1 , wherein the polymers, oligomers, or mixtures thereof are polyolefins and wherein said polyolefins are selected from the group consisting of high density polyethylene, low density polyethylene, polypropylene, linear low density polyethylene, polyethylene-polypropylene-copolymers, polystyrene, and mixtures thereof.

5. The process of claim 1 , wherein said contacting is carried out at a temperature sufficient to melt the polymers, oligomers, or mixtures thereof.

6. The process of claim 1 , wherein said contacting is carried out under atmospheric pressure or under a vacuum.

7. The process of claim 1 , wherein said contacting is carried out under conditions effective to form the shorter alkanes and comprises:

adding an alcohol or water to the reaction mixture to form the shorter alkanes.

8. The process of claim 1 , wherein said contacting is carried out under conditions effective to form shorter carboxylic acids and comprises:

adding carbon dioxide to the reaction mixture under conditions effective to form the shorter carboxylic acids.

9. The process of claim 1 , wherein said contacting is carried out under conditions effective to form the shorter alcohols and comprises:

adding oxygen to the reaction mixture to form the shorter alcohols.

10. The process of claim 1 , wherein said contacting is carried out under conditions effective to form shorter alkyl halides and comprises:

adding a halogen to the reaction mixture to form the shorter alkyl halides.

11. The process of claim 1 , wherein said contacting is carried out under conditions effective to form the shorter aldehydes and comprises:

adding an orthoester to the reaction mixture to form the shorter aldehydes.

12. The process of claim 1 , wherein the molar ratio of the compound of formula (I) to the catalyst of formula (II) ranges from 3:1 to 20:1.

13. A process comprising:

providing one or more polymers, oligomers, or mixtures thereof;

providing a compound of formula (I):

Al(R 1 ) 3   (I),

wherein

R 1 is independently selected at each occurrence thereof from the group consisting of H, aryl, C 1 -C 8 alkyl, and C 1 -C 8 alkoxy;

contacting the polymers, oligomers, or mixtures thereof with the compound of formula (I), as a reaction mixture, in the presence of a catalyst having a formula (II):

Met(R 2 ) n @support  (II),

wherein

Met is a metal selected from the group consisting of zirconium, titanium, hafnium, scandium, yttrium, lanthanum, and lutetium;

R 2 is independently selected at each occurrence thereof from the group consisting of H, C 1 -C 10 alkyl, C 5 -C 10 alkoxy, and BH 4 ;

n is an integer ranging from 1 to 3; and

support is selected from the group consisting of silica, silica/alumina, and zeolites;

under conditions effective to form an aluminum alkyl compound of formula (III):

Al(R 1 ) 3-n (R 3 ) n   (III),

wherein

R 3 is independently selected at each occurrence thereof from C 12 -C 60 alkyls, which are shorter than the polymers, the oligomers, or the mixtures thereof; and

n is an integer ranging from one to three.

14. The process of claim 13 , wherein the catalyst of formula (II) is selected from the group consisting of Zr(CH 2 CMe 3 ) n @SiAlO x , Zr(OCH 2 CMe 3 ) n @SiAlO x , Zr(CH 2 CMe 3 ) n @SiO 2 , Zr(H) n @SiO 2 , and Zr(H) n @SiAlO x , wherein n is an integer ranging from 1-3.

15. The process of claim 13 , wherein the compound of formula (I) is selected from the group consisting of AliBu 3 , AlEt 3 , AlMe 3 , AlPh 3 , Al(C 8 H 17 ) 3 , and AlH 3 .

16. The process of claim 13 , wherein the polymers, oligomers, or mixtures thereof are polyolefins and wherein said polyolefins are selected from the group consisting of high density polyethylene, low density polyethylene, polypropylene, linear low density polyethylene, polyethylene-polypropylene-copolymers, polystyrene, and mixtures thereof.

17. The process of claim 13 , wherein said contacting is carried out at a temperature sufficient to melt the polymers, oligomers, or mixtures thereof.

18. The process of claim 13 , wherein said contacting is carried out under atmospheric pressure or under a vacuum.

19. The process according to claim 1 , wherein Met is a metal selected from the group consisting of zirconium, titanium, yttrium, lanthanum, and lutetium.

20. The process according to claim 13 , wherein Met is a metal selected from the group consisting of zirconium, titanium, yttrium, lanthanum, and lutetium.