We claim:
1. A polymerization process comprising contacting:
(a) a catalyst system;
(b) monomers; and
(c) an antistatic agent;
in a reactor under polymerization conditions;
wherein the antistatic agent is present from about 0.05 to about 200 ppm based on the weight of the monomers introduced into the reactor.
2. The polymerization process of claim 1, wherein the antistatic agent is contacted with a scavenger prior to polymerization.
3. The polymerization process of claim 2, wherein the scavenger comprises an aluminum alkyl compound.
4. The polymerization process of claim 3, wherein the aluminum alkyl compound is selected from the group consisting of triethylaluminum, trimethylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, diethyl aluminum chloride, and mixtures thereof.
5. The polymerization process of claim 4, wherein the aluminum alkyl compound is triethylaluminum.
6. The polymerization process of claim 1, wherein the antistatic agent comprises a polysulfone copolymer, a polymeric polyamine, an oil-soluble sulfonic acid, or mixtures thereof, with or without a solvent.
7. The polymerization process of claim 1, wherein the antistatic agent is present from about 0.1 to about 40 ppm based on the weight of the monomers introduced into the reactor.
8. The polymerization process of claim 1, wherein the antistatic agent is present from about 0.1 to about 5 ppm based on the weight of the monomers introduced into the reactor.
9. The polymerization process of claim 1, wherein the antistatic agent is present from about 0.3 to about 0.8 ppm based on the weight of the monomers introduced into the reactor.
10. The polymerization process of claim 1, wherein the catalyst system comprises a supported metallocene catalyst system.
11. The polymerization process of claim 1, wherein the catalyst system comprises a supported metallocene catalyst system comprising a support and a metallocene, the metallocene represented by the following:
6
wherein M is a metal of Group 4, 5, or 6 of the Periodic Table;
R1 and R2 are identical or different, and are one of a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C10 aryl group, a C6-C10 aryloxy group, a C2-C10 alkenyl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, or a halogen atom;
R5 and R6 are identical or different, and are one of a halogen atom, a C1-C10 alkyl group, which may be halogenated, a C6-C10 aryl group, which may be halogenated, a C2-C10 alkenyl group, a C7-C40-arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a NR215, SR15, OR15, OSiR315 or PR215 radical, wherein R15 is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group;
R7 is
7
B(R11), Al(R1 l), Ge, Sn, O, S, SO, SO2, N(R11), CO, P(R11), or P(O)(R11);
wherein R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 fluoroalkyl group, a C6-C30 aryl group, a C6-C30 fluoroaryl group, a C1-C20 alkoxy group, a C2-C20 alkenyl group, a C7-C40 arylalkyl group, a C8-C40 arylalkenyl group, a C7-C40 alkylaryl group, or R11 and R12, or R11 and R13, together with the atoms binding them, can form ring systems;
M2 is silicon, germanium or tin;
R8 and R9 are identical or different and have the meanings stated for R11;
m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2; and
the radicals R3, R4, and R10 are identical or different and have the meanings stated for R11, R12 and R13.
12. The polymerization process of claim 11, wherein the support is a fluorided support.
13. The polymerization process of claim 1, wherein the catalyst system comprises a metallocene catalyst system comprising a metallocene selected from the group consisting of Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) zirconium dimethyl; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-ethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) zirconium dichloride; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-ethyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) zirconium dichloride; and mixtures thereof.
14. The polymerization process of claim 13, wherein the catalyst system further comprises a support.
15. The polymerization process of claim 14, wherein the support is a fluorided support.
16. A contact product of components comprising:
(a) a catalyst system;
(b) an antistatic agent; and
(c) monomers;
wherein the antistatic agent is present from about 0.05 to about 200 ppm based on the weight of the monomers.
17. The contact product of claim 16, wherein the antistatic agent is contacted with a scavenger prior to polymerization.
18. The contact product of claim 17, wherein the scavenger comprises an aluminum alkyl compound.
19. The contact product of claim 18, wherein the aluminum alkyl compound is selected from the group consisting of triethylaluminum, trimethylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, diethyl aluminum chloride, and mixtures thereof.
20. The contact product of claim 19, wherein the aluminum alkyl compound is triethylaluminum.
21. The contact product of claim 16, wherein the antistatic agent comprises a polysulfone copolymer, a polymeric polyamine, an oil-soluble sulfonic acid, or mixtures thereof, with or without a solvent.
22. The contact product of claim 16, wherein the antistatic agent is present from about 0.1 to about 40 ppm based on the weight of the monomers.
23. The contact product of claim 16, wherein the antistatic agent is present from about 0.1 to about 5 ppm based on the weight of the monomers.
24. The contact product of claim 16, wherein the antistatic agent is present from about 0.3 to about 0.8 ppm based on the weight of the monomers.
25. The contact product of claim 16, wherein the catalyst system comprises a supported metallocene catalyst system.
26. The contact product of claim 16, wherein the catalyst system comprises a supported metallocene catalyst system comprising a support and a metallocene, the metallocene represented by the following:
8
wherein M is a metal of Group 4, 5, or 6 of the Periodic Table;
R1 and R2 are identical or different, and are one of a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C10 aryl group, a C6-C10 aryloxy group, a C2-C10 alkenyl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, or a halogen atom;
R5 and R6 are identical or different, and are one of a halogen atom, a C1-C10 alkyl group, which may be halogenated, a C6-C10 aryl group, which may be halogenated, a C2-C10 alkenyl group, a C7-C40-arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a NR215, SR15, OR15, OSiR315 or PR215 radical, wherein R15 is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group;
R7 is
9
B(R11), Al(R11), Ge, Sn, O, S, SO, SO2, N(R11), CO P(R11), or P(O)(R11);
wherein R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 fluoroalkyl group, a C6-C30 aryl group, a C6-C30 fluoroaryl group, a C1-C20 alkoxy group, a C2-C20 alkenyl group, a C7-C40 arylalkyl group, a C8-C40 arylalkenyl group, a C7-C40 alkylaryl group, or R1 and R12, or R1 and R13, together with the atoms binding them, can form ring systems;
M2 is silicon, germanium or tin;
R8 and R9 are identical or different and have the meanings stated for R11;
m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2; and
the radicals R3, R4, and R11 are identical or different and have the meanings stated for R11, R12 and R13.
27. The contact product of claim 26, wherein the support is a fluorided support.
28. The contact product of claim 16, wherein the catalyst system comprises a metallocene catalyst system comprising a metallocene selected from the group consisting of Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) zirconium dimethyl; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-ethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) zirconium dichloride; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-ethyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) zirconium dichloride; and mixtures thereof.
29. The contact product of claim 28, wherein the catalyst system further comprises a support.
30. The contact product of claim 29, wherein the support is a fluorided support.
31. The contact product of claim 16, wherein the contact product comprises a propylene homopolymer or copolymer.
32. A process for the continuous gas phase polymerization of propylene polymers in a reactor, the process comprising contacting:
(a) a catalyst system comprising a metallocene catalyst system;
(b) monomers; and
(c) an antistatic agent comprising a polysulfone copolymer, a polymeric polyamine, an oil-soluble sulfonic acid, or mixtures thereof, with or without a solvent;
wherein the antistatic agent is present from about 0.05 to about 200 ppm based on the weight of the monomers introduced into the reactor.
33. The process of claim 32, wherein the antistatic agent is contacted with a scavenger prior to polymerization.
34. The process of claim 33, wherein the scavenger comprises an aluminum alkyl compound.
35. The process of claim 34, wherein the aluminum alkyl compound is selected from the group consisting of triethylaluminum, trimethylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, diethyl aluminum chloride, and mixtures thereof.
36. The process of claim 35, wherein the aluminum alkyl compound is triethylaluminum.
37. The process of claim 32, wherein the antistatic agent is present from about 0.1 to about 40 ppm based on the weight of the monomers introduced into the reactor.
38. The process of claim 32, wherein the antistatic agent is present from about 0.1 to about 5 ppm based on the weight of the monomers introduced into the reactor.
39. The process of claim 32, wherein the antistatic agent is present from about 0.3 to about 0.8 ppm based on the weight of the monomers introduced into the reactor.
40. The process of claim 32, wherein the metallocene catalyst system comprises a supported metallocene catalyst system.
41. The process of claim 32, wherein the metallocene catalyst system comprises a support and a metallocene, the metallocene represented by the following:
10
wherein M is a metal of Group 4, 5, or 6 of the Periodic Table;
R1 and R2 are identical or different, and are one of a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C10 aryl group, a C6-C10 aryloxy group, a C2-C10 alkenyl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, or a halogen atom;
R5 and R6 are identical or different, and are one of a halogen atom, a C1-C10 alkyl group, which may be halogenated, a C6-C10 aryl group, which may be halogenated, a C2-C10 alkenyl group, a C7-C40-arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a NR215, SR15, OR15, OSiR315 or PR215 radical, wherein R15 is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group;
R7 is
11
B(R1 l)-, Al(R11), Ge, Sn, O, S, SO, SO2, N(R1 l)-, CO, P(R11), or P(O)(R11);
wherein R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 fluoroalkyl group, a C6-C30 aryl group, a C6-C30 fluoroaryl group, a C1-C20 alkoxy group, a C2-C20 alkenyl group, a C7-C40 arylalkyl group, a C8-C40 arylalkenyl group, a C7-C40 alkylaryl group, or R11 and R12, or R1 and R13, together with the atoms binding them, can form ring systems;
M2 is silicon, germanium or tin;
R8 and R9 are identical or different and have the meanings stated for R11;
m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2; and
the radicals R3, R4, and R10 are identical or different and have the meanings stated for R11, R12 and R13.
42. The process of claim 41, wherein the support is a fluorided support.
43. The process of claim 32, wherein the metallocene catalyst system comprises a metallocene selected from the group consisting of Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) zirconium dimethyl; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-ethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) zirconium dichloride; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-ethyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) zirconium dichloride; and mixtures thereof.
44. The process of claim 43, wherein the metallocene catalyst system further comprises a support.
45. The process of claim 44, wherein the support is a fluorided support.
46. A propylene homopolymer or copolymer produced by the process of claim 32.
47. A process for the continuous slurry polymerization to produce propylene polymers in a reactor, the process comprising contacting:
(a) a catalyst system comprising a metallocene catalyst system;
(b) monomers; and
(c) an antistatic agent comprising at least one of the components selected from the group consisting of a polysulfone copolymer, a polymeric polyamine, oil-soluble sulfonic acid, or mixtures thereof, with or without a solvent;
wherein the antistatic agent is present from about 0.05 to about 200 ppm based on the weight of the monomers introduced into the reactor.
48. The polymerization process of claim 47, wherein the antistatic agent is contacted with a scavenger prior to polymerization.
49. The polymerization process of claim 48, wherein the scavenger comprises an aluminum alkyl compound.
50. The polymerization process of claim 49, wherein the aluminum alkyl compound is selected from the group consisting of triethylaluminum, trimethylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, diethyl aluminum chloride, and mixtures thereof.
51. The polymerization process of claim 50, wherein the aluminum alkyl compound is triethylaluminum.
52. The polymerization process of claim 47, wherein the antistatic agent is present from about 0.1 to about 40 ppm based on the weight of the monomers introduced into the reactor.
53. The polymerization process of claim 47, wherein the antistatic agent is present from about 0.1 to about 5 ppm based on the weight of the monomers introduced into the reactor.
54. The polymerization process of claim 47, wherein the antistatic agent is present from about 0.3 to about 0.8 ppm based on the weight of the monomers introduced into the reactor.
55. The polymerization process of claim 47, wherein the metallocene catalyst system comprises a supported metallocene catalyst system.
56. The polymerization process of claim 47, wherein the metallocene catalyst system comprises a support and a metallocene, the metallocene represented by the following:
12
wherein M is a metal of Group 4, 5, or 6 of the Periodic Table;
R1 and R2 are identical or different, and are one of a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C10 aryl group, a C6-C10 aryloxy group, a C2-C10 alkenyl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, or a halogen atom;
R5 and R6 are identical or different, and are one of a halogen atom, a C1-C10 alkyl group, which may be halogenated, a C6-C10 aryl group, which may be halogenated, a C2-C10 alkenyl group, a C7-C40-arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a NR215, SR15, OR15, OSiR315 or PR215 radical, wherein R15 is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group;
R7 is
13
B(R11), Al(R11), Ge, Sn, O, S, SO, SO2, N(R11), CO, P(R11), or P(O)(R11);
wherein R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 fluoroalkyl group, a C6-C30 aryl group, a C6-C30 fluoroaryl group, a C1-C20 alkoxy group, a C2-C20 alkenyl group, a C7-C40 arylalkyl group, a C8-C40 arylalkenyl group, a C7-C40 alkylaryl group, or R11 and R12, or R11 and R13, together with the atoms binding them, can form ring systems;
M2 is silicon, germanium or tin;
R8 and R9 are identical or different and have the meanings stated for R1;
m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2; and
the radicals R3, R4, and R10 are identical or different and have the meanings stated for R11, R12 and R13.
57. The polymerization process of claim 56, wherein the support is a fluorided support.
58. The polymerization process of claim 47, wherein the metallocene catalyst system comprises a metallocene selected from the group consisting of Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) zirconium dimethyl; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-ethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) zirconium dichloride; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-ethyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) zirconium dichloride; and mixtures thereof.
59. The polymerization process of claim 58, wherein the metallocene catalyst system further comprises a support.
60. The polymerization process of claim 59, wherein the support is a fluorided support.
61. A homopolymer or copolymer produced by the process of claim 47.
62. A method to reduce fouling in a reactor comprising the step of:
(a) adding propylene monomers into the reactor;
(b) adding a catalyst system comprising a metallocene catalyst system;
(c) adding an antistatic agent; and
(d) forming a polymer in the reactor;
wherein the antistatic agent is present from about 0.05 to about 200 ppm based on the weight of the propylene monomers introduced into the reactor.
63. The method of claim 62, wherein the antistatic agent is contacted with a scavenger prior to polymerization.
64. The method of claim 63, wherein the scavenger comprises an aluminum alkyl compound.
65. The method of claim 64, wherein the aluminum alkyl compound is selected from the group consisting of triethylaluminum, trimethylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, diethyl aluminum chloride, and mixtures thereof.
66. The method of claim 65, wherein the aluminum alkyl compound is triethylaluminum.
67. The method of claim 62, wherein the antistatic agent comprises a polysulfone copolymer, a polymeric polyamine, an oil-soluble sulfonic acid, or mixtures thereof, with or without a solvent.
68. The method of claim 62, wherein the antistatic agent is present from about 0.1 to about 40 ppm based on the weight of the propylene monomers introduced into the reactor.
69. The method of claim 62, wherein the antistatic agent is present from about 0.1 to about 5 ppm based on the weight of the propylene monomers introduced into the reactor.
70. The method of claim 62, wherein the antistatic agent is present from about 0.3 to about 0.8 ppm based on the weight of the propylene monomers introduced into the reactor.
71. The method of claim 62, wherein the metallocene catalyst system comprises a supported metallocene catalyst system.
72. The method of claim 62, wherein the metallocene catalyst system comprises a support and a metallocene, the metallocene represented by the following:
14
wherein M is a metal of Group 4, 5, or 6 of the Periodic Table;
R1 and R2 are identical or different, and are one of a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C10 aryl group, a C6-C10 aryloxy group, a C2-C10 alkenyl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, or a halogen atom;
R5 and R6 are identical or different, and are one of a halogen atom, a C1-C10 alkyl group, which may be halogenated, a C6-C10 aryl group, which may be halogenated, a C2-C10 alkenyl group, a C7-C40-arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a NR215, SR15, OR15, OSiR315 or PR215 radical, wherein R15 is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group;
R7 is
15
B(R1 l)-, Al(R1 l)-, Ge, Sn, O, S, SO, SO2, N(R11), CO, P(R11), or P(O)(R11);
wherein R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 fluoroalkyl group, a C6-C30 aryl group, a C6-C30 fluoroaryl group, a C1-C20 alkoxy group, a C2-C20 alkenyl group, a C7-C40 arylalkyl group, a C8-C40 arylalkenyl group, a C7-C40 alkylaryl group, or R11 and R12, or R11 and R13, together with the atoms binding them, can form ring systems;
M2 is silicon, germanium or tin;
R8 and R9 are identical or different and have the meanings stated for R11;
m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2; and
the radicals R3, R4, and R10 are identical or different and have the meanings stated for R11, R12 and R13.
73. The method of claim 72, wherein the support is a fluorided support.
74. The method of claim 62, wherein the metallocene catalyst system comprises a metallocene selected from the group consisting of Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) zirconium dimethyl; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-ethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) zirconium dichloride; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-ethyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) zirconium dichloride; and mixtures thereof.
75. The method of claim 74, wherein the metallocene catalyst system further comprises a support.
76. The method of claim 75, wherein the support is a fluorided support.
77. The method of claim 62, wherein the polymer comprises a propylene homopolymer or copolymer.
78. A continuous process for polymerizing olefin monomers in a reactor under polymerization conditions, the continuous process comprising the steps of:
(a) adding olefin monomers into the reactor;
(b) adding a catalyst system;
(c) adding an antistatic agent; and
(d) forming a polymer in the reactor;
wherein the antistatic agent is present from about 0.05 to about 200 ppm based on the weight of the olefin monomers introduced into the reactor.
79. The continuous process of claim 78, wherein the antistatic agent is contacted with a scavenger prior to polymerization.
80. The continuous process of claim 79, wherein the scavenger comprises an aluminum alkyl compound.
81. The continuous process of claim 80, wherein the aluminum alkyl compound is selected from the group consisting of triethylaluminum, trimethylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, diethyl aluminum chloride, and mixtures thereof.
82. The continuous process of claim 81, wherein the aluminum alkyl compound is triethylaluminum.
83. The continuous process of claim 78, wherein the antistatic agent comprises a polysulfone copolymer, a polymeric polyamine, an oil-soluble sulfonic acid, or mixtures thereof, with or without a solvent.
84. The continuous process of claim 78, wherein the antistatic agent is present from about 0.1 to about 40 ppm based on the weight of the olefin monomers introduced into the reactor.
85. The continuous process of claim 78, wherein the antistatic agent is present from about 0.1 to about 5 ppm based on the weight of the olefin monomers introduced into the reactor.
86. The continuous process of claim 78, wherein the antistatic agent is present from about 0.3 to about 0.8 ppm based on the weight of the olefin monomers introduced into the reactor.
87. The continuous process of claim 78, wherein the catalyst system comprises a supported metallocene catalyst system.
88. The continuous process of claim 78, wherein the catalyst system comprises a supported metallocene catalyst system comprising a support and a metallocene, the metallocene represented by the following:
16
wherein M is a metal of Group 4, 5, or 6 of the Periodic Table;
R1 and R2 are identical or different, and are one of a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C10 aryl group, a C6-C10 aryloxy group, a C2-C10 alkenyl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, or a halogen atom;
R5 and R6 are identical or different, and are one of a halogen atom, a C1-C10 alkyl group, which may be halogenated, a C6-C10 aryl group, which may be halogenated, a C2-C10 alkenyl group, a C7-C40-arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a NR215, SR15, OR15, OSiR315 or PR215 radical, wherein R15 is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group;
R7 is
17
B(R11), Al(R11), Ge, Sn, O, S, SO, SO2, N(R11), CO, P(R11), or P(O)(R11);
wherein R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 fluoroalkyl group, a C6-C30 aryl group, a C6-C30 fluoroaryl group, a C1-C20 alkoxy group, a C2-C20 alkenyl group, a C7-C40 arylalkyl group, a C8-C40 arylalkenyl group, a C7-C40 alkylaryl group, or R11 and R12, or R11 and R13, together with the atoms binding them, can form ring systems;
M2 is silicon, germanium or tin;
R8 and R9 are identical or different and have the meanings stated for R11;
m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2; and
the radicals R3, R4, and R10 are identical or different and have the meanings stated for R11, R12 and R13.
89. The continuous process of claim 88, wherein the support is a fluorided support.
90. The continuous process of claim 78, wherein the catalyst system comprises a metallocene catalyst system comprising a metallocene selected from the group consisting of Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) zirconium dimethyl; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-methyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2-ethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) zirconium dichloride; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-methyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2-ethyl-1-indenyl) zirconium dichloride; Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) zirconium dichloride; and mixtures thereof.
91. The continuous process of claim 90, wherein the catalyst system further comprises a support.
92. The continuous process of claim 91, wherein the support is a fluorided support.
93. The continuous process of claim 78, wherein the polymer comprises a propylene homopolymer or copolymer.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. An apparatus comprising:
a light emitter;
a surround about the light emitter, the surround comprising one or more layers of silicone; and
plant materials internally encapsulated within and throughout the one or more layers of silicone.
2. The apparatus of claim 1, wherein the plant materials are visible through the one of more layers of silicone and provide a scent.
3. The apparatus of claim 2, wherein the plant materials comprise coffee grains.
4. The apparatus of claim 1, wherein the plant materials comprise seeds.
5. The apparatus of claim 1, wherein the plant materials comprise poppy seeds.
6. The apparatus of claim 1, wherein the plant materials comprise spices.
7. The apparatus of claim 1, wherein the spices are visible through the one of more layers of silicone and provide a scent.
8. The apparatus of claim 1, wherein the light emitter comprises an incandescent bulb having an externally threaded end.
9. The apparatus of claim 1, when the light emitter comprises one or more light emitting diodes.
10. The apparatus of claim 1, wherein the plant materials comprise ground or cut flower parts.
11. The apparatus of claim 1, wherein the one of more layers of silicone have varying thicknesses extending from the light emitter to form a three-dimensional shape about the light emitter.
12. The apparatus of claim 1, wherein the surround is colored.
13. The apparatus of claim 1, wherein the surround is formed from a first silicone and a second distinct silicone.
14. The apparatus of claim 1, wherein the first silicone is a first color and wherein the second silicone is a second color.
15. The apparatus of claim 1, wherein the first silicone has a first scent and wherein the second silicone has a second scent.
16. The apparatus of claim 1, wherein the surround has a shape associated with a holiday.
17. The apparatus of claim 1, wherein the surround has a shape selected from a group of shapes consisting of:
one or more stars, one or more hearts, one or more eggs, one or more crosses, one or more pumpkins, one or more bunnies, one or more Christmas trees, one or more Santas, one or more bells, one or more candy canes, one or more candles, one or more snowmen, one or more snowflakes and one or more shamrocks.
18. A method comprising:
internally encapsulating plant materials in silicone; and
forming a three-dimensional shape about a bulb only light emitter from the silicone with the internally encapsulated plant material.