What is claimed is:
1. A process for the polymerization of olefins, comprising the step of contacting, at a temperature of about 100 C. to about 200 C., one or more monomers selected from the group consisting of ethylene and an olefin of the formula H2CCH(CH2)nH (XXII), and a Cr, Mn, V, Ti, Zr or Hf complex of an anion of the formula (I)
25
wherein:
R1 is hydrocarbyl or substituted hydrocarbyl, R2 is hydrogen, hydrocarbyl or substituted hydrocarbyl, and R3 is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that R1 and R2 taken together may be orthoarylene or substituted ortho-arylene, or R1, R2 and R3 taken together may form one or more rings;
Z is a bridging group of the formula (II), (III) or (IV)
26
Q is nitrogen, oxygen, phosphorous or sulfur, provided that when Z is (II), Q is oxygen;
R4 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that when Q is oxygen or sulfur R4 is not present;
R6 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R3 and R6 together may form a ring;
R7 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R3, R6 and R7 together may form an aromatic ring, or R6 and R7 taken together may form a ring;
R8 is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R9 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R4 and R9 taken together may be part of a double bond to an imino nitrogen atom, or R8 and R9 taken together may form a carbonyl with the carbon to which they are attached, or R8 and R9 taken together may form a ring, or R4 and R9 taken together may form a ring, or R4, R8 and R9 taken together may form a ring, or R6, R7, R8 and R9 taken together may form an aromatic ring;
R10, R11, R12 and R13 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R10, R11, R12 and R13 taken together may be ortho-arylene;
R14 and R15 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R14 and R15 taken together may form a carbonyl with the carbon to which they are attached, or R12, R13, R14, and R15 taken together may form an o-arylene group, or R10, R11, R12, R13, R14, and R15 taken together may form a fused aromatic ring system, or R13 and R14 taken together may form a ring;
R20 and R21 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or R20 and R21 taken together may form a ring;
each R22 is individually hydrocarbyl, oxygen or alkoxy, provided that when R22 is oxygen, two of R22 are taken together to form TO;
n is an integer of 1 or more;
T is phosphorous or sulfur whose oxidation state is 3 or greater; and
x is equal to the oxidation state of T minus 2.
2. The process as recited in claim 1, wherein the monomer is ethylene.
3. The process as recited in claim 1, wherein the transition metal is selected from the group consisting of Zr and Ti.
4. The process as recited in claim 1, wherein R1 and R2 taken together are o-arylene, Z is a group of the formula (III), Q is oxygen, and R6, R7, R8 and R9 taken together form an aromatic ring.
5. The process as recited in claim 4, wherein (I) has the formula
27
wherein R24, R25, R26, R27, R29, R30, R31 and R32 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, and R28 is hydrogen, hydrocarbyl, or substituted hydrocarbyl, provided that any two of R24, R25, R26, R27, R29, R30, R31 and R32 vicinal to one another may be taken together to form a ring, and that R27 and R28 may be taken together to form a ring, or R28 and R29 may be taken together to form a ring.
6. A process for the polymerization of olefins, comprising the step of contacting, at a temperature of about 100 C. to about 200 C., one or more monomers selected from the group consisting of ethylene and H2CCH(CH2)nH (XXII), with a compound of the formula (V)
28
wherein:
R1 is hydrocarbyl or substituted hydrocarbyl, R2 is hydrogen, hydrocarbyl or substituted hydrocarbyl, and R3 is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that R1 and R2 taken together may be orthoarylene or substituted ortho-arylene, or R1, R2 and R3 taken together may form one or more rings;
Z is a bridging group of the formula (II), (III) or (IV)
29
Q is nitrogen, oxygen, phosphorous or sulfur, provided that when Z is (II), Q is oxygen;
R4 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that when Q is oxygen or sulfur R4 is not present;
R6 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R3 and R6 taken together may form a ring;
R7 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R3, R6 and R7 taken together may form an aromatic ring, or R6 and R7 taken together may form a ring;
R8 is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R9 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R4 and R9 taken together may be part of a double bond to an imino nitrogen atom, or R8 and R9 taken together may form a carbonyl with the carbon to which they are attached, or R8 and R9 taken together may form a ring, or R4 and R9 taken together may form a ring, or R4, R8 and R9 taken together may form a ring, or R6, R7, R8 and R9 taken together may form an aromatic ring;
R10, R11, R12 and R13 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R10, R11, R12 and R13 taken together may be ortho-arylene;
R14 and R15 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R14 and R15 taken together may form a carbonyl with the carbon to which they are attached, or R12, R13, R14, and R15 taken together may form an o-arylene group, or R10, R11, R12, R13, R14, and R15 taken together may form a fused aromatic ring system, or R13 and R14 taken together may form a ring;
R20 and R21 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or R20 and R21 taken together may form a ring;
each R22 is individually hydrocarbyl, oxygen or alkoxy, provided that when R22 is oxygen, two of R22 are taken together to form TO;
n is an integer of 1 or more;
T is phosphorous or sulfur whose oxidation state is 3 or greater;
x is equal to the oxidation state of T minus 2;
M is Ti, Zr, Hf, V, Mn or Cr;
m is an integer equal to the valence of M minus 2; and
each L1 is independently a monodentate monoanionic ligand and at least for one of L1 an ethylene molecule may insert between L1 and M, and L2 is a monodentate neutral ligand which may be displaced by ethylene or an empty coordination site, provided that an L1 and L2 taken together may be a monoanionic polydentate ligand and at least for one of these monoanionic polydentate ligands ethylene may insert between said monoanionic polydentate ligand and M.
7. The process as recited in claim 6, wherein the monomer is ethylene.
8. The process as recited in claim 6, wherein the transition metal is selected from the group consisting of Zr and Ti.
9. The process as recited in claim 6, wherein R1 and R2 taken together are o-arylene, Z is a group of the formula (III), Q is oxygen, and R6, R7, R8 and R9 taken together form an aromatic ring.
10. The process as recited in claim 6, wherein (V) has the formula
30
wherein R24, R25, R26, R27, R29, R30, R31 and R32 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, and R28 is hydrogen, hydrocarbyl, or substituted hydrocarbyl, provided that any two of R24, R25, R26, R27, R29, R30, R31 and R32 vicinal to one another may be taken together to form a ring, and that R27 and R28 may be taken together to form a ring, or R28 and R29 may be taken together to form a ring.
11. The process as recited in claim 6, wherein the monomers and compound of the formula (V) are contacted in the further presence of a catalyst activator.
12. A compound of the formula (VI)
31
wherein:
R1 is hydrocarbyl or substituted hydrocarbyl, R2 is hydrogen, hydrocarbyl or substituted hydrocarbyl, and R3 is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that R1 and R2 taken together may be orthoarylene or substituted ortho-arylene, or R1, R2 and R3 taken together may form one or more rings;
Z is a bridging group of the formula (II), (III) or (IV)
32
Q is nitrogen, oxygen, phosphorous or sulfur, provided that when Z is (II), Q is oxygen;
R4 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that when Q is oxygen or sulfur R4 is not present;
R6 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R3 and R6 taken together may form a ring;
R7 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R3, R6 and R7 taken together may form an aromatic ring, or R6 and R7 taken together may form a ring;
R8 is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R9 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R4 and R9 taken together may be part of a double bond to an imino nitrogen atom, or R8 and R9 taken together may form a carbonyl with the carbon to which they are attached, or R8 and R9 taken together may form a ring, or R4 and R9 taken together may form a ring, or R4, R8 and R9 taken together may form a ring, or R6, R7, R8 and R9 taken together may form an aromatic ring;
R10, R11, R12 and R13 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R10, R11, R12 and R13 taken together may be ortho-arylene;
R14 and R15 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R14 and R15 taken together may form a carbonyl with the carbon to which they are attached, or R12, R13, R14 and R15 taken together may form an o-arylene group, or R10, R11, R12, R13, R14, and R15 taken together may form a fused aromatic ring system, or R13 and R14 taken together may form a ring;
R20 and R21 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or R20 and R21 taken together may form a ring;
each R22 is individually hydrocarbyl, oxygen or alkoxy, provided that when R22 is oxygen, two of R22 are taken together to form TO;
n is an integer of 1 or more;
T is phosphorous or sulfur whose oxidation state is 3 or greater;
x is equal to the oxidation state of T minus 2;
M is Ti, Zr, Hf, V, Mn or Cr;
m is an integer equal to the valence of M minus 2; and
p is 0 or 1; and
each L3 is independently a monodentate monoanionic ligand, and L4 is a monodentate neutral ligand or an empty coordination site, provided that an L3 and L4 taken together may be a monoanionic bidentate ligand.
13. The compound as recited in claim 12, wherein M is selected from the group consisting of Zr and Ti.
14. The compound as recited in claim 12, wherein R1 and R2 taken together are o-arylene, Z is a group of the formula (III), Q is oxygen, and R6, R7, R8 and R9 taken together form an aromatic ring.
15. The compound as recited in claim 12, wherein (VI) has the formula
33
wherein R24, R25, R26, R27, R29, R30, R31 and R32 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, and R28 is hydrogen, hydrocarbyl, or substituted hydrocarbyl, provided that any two of R24, R25, R26, R27, R28, R29, R30 and R32 vicinal to one another may be taken together to form a ring, and that R27 and R28 may be taken together to form a ring, or R28 and R29 may be taken together to form a ring.
16. A polymerization catalyst component comprising a Ti, Zr, Hf, V, Mn or Cr complex of an anion of the formula (I)
34
wherein:
R1 is hydrocarbyl or substituted hydrocarbyl, R2 is hydrogen, hydrocarbyl or substituted hydrocarbyl, and R3 is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that R1 and R2 taken together may be orthoarylene or substituted ortho-arylene, or R1, R2 and R taken together may form one or more rings;
Z is a bridging group of the formula (II), (III) or (IV)
35
Q is nitrogen, oxygen, phosphorous or sulfur, provided that when Z is (II), Q is oxygen;
R4 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that when Q is oxygen or sulfur R4 is not present;
R6 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R3 and R6 together may form a ring;
R7 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R3, R6 and R7 together may form an aromatic ring, or R6 and R7 taken together may form a ring;
R8 is hydrogen, hydrocarbyl or substituted hydrocarbyl;
R9 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R4 and R9 taken together may be part of a double bond to an imino nitrogen atom, or R8 and R9 taken together may form a carbonyl with the carbon to which they are attached, or R8 and R9 taken together may form a ring, or R4 and R9 taken together may form a ring, or R4, R8 and R9 taken together may form a ring, or R6, R7, R8 and R9 taken together may form an aromatic ring;
R10, R11, R12 and R13 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R10, R11, R12 and R13 taken together may be ortho-arylene;
R14 and R15 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R14 and R15 taken together may form a carbonyl with the carbon to which they are attached, or R12, R13, R14, and R15 taken together may form an o-arylene group, or R10, R11, R12, R13, R14 and R15 taken together may form a fused aromatic ring system, or R13 and R14 taken together may form a ring;
R20 and R21 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or R20 and R21 taken together may form a ring;
each R22 is individually hydrocarbyl, oxygen or alkoxy, provided that when R22 is oxygen, two of R22 are taken together to form TO;
n is an integer of 1 or more;
T is phosphorous or sulfur whose oxidation state is 3 or greater; and
x is equal to the oxidation state of T minus 2.
17. The polymerization catalyst component as recited in claim 16, wherein the transition metal is selected from the group consisting of Zr and Ti.
18. The polymerization catalyst component as recited in claim 16, wherein R1 and R2 taken together are o-arylene, Z is a group of the formula (III), Q is oxygen, and R6, R7, R8 and R9 taken together form an aromatic ring.
19. The polymerization catalyst component as recited in claim 18, wherein (I) has the formula
36
wherein R24, R25, R26,l R27, R29, R30, R31 and R32 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, and R28 is hydrogen, hydrocarbyl, or substituted hydrocarbyl, provided that any two of R24, R25, R26, R27, R29, R30, R31 and R32 vicinal to one another may be taken together to form a ring, and that R27 and R28 may be taken together to form a ring, or R28 and R29 may be taken together to form a ring.
20. The polymerization catalyst component as recited in claim 16, further comprising a catalyst activator.
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. A simulated smoking device for non-burning use comprises:
a vessel defining a hollow interior;
an insert located within said interior being adapted to carry an aromatic substance thereon;
an oblong implement sized and shaped to penetrate into said interior and having a first abrasive end to scrape against said substance, thereby releasing said substance.
2. The device of claim 1, wherein said insert is formed into a tube removably mounted within said interior.
3. The device of claim 1, wherein said interior is divided by a septum into a first chamber and a second chamber; wherein said aromatic substance is located within said first chamber.
4. The device of claim 3, which further comprises a smoke-simulating powder located in said second chamber.
5. The device of claim 3, wherein said septum is penetrated by a valved opening encouraging a unidirectional flow therethrough.
6. The device of claim 5, wherein said device further comprises a spline located within said second chamber.
7. The device of claim 5, wherein said unidirectional flow goes from said first chamber to said second chamber, thereby allowing exhalation.
8. The device of claim 4, wherein a portion of said smoke-simulating powder is selected from the group consisting of talc and diatomaceous earth.
9. The device of claim 1, wherein said aromatic substance is formed to have a plurality of spaced apart thickened portions thereby increasing the surface area of said aromatic substance.
10. The device of claim 9, wherein said plurality of thickened portions are formed by a helicoidal bead.
11. The device of claim 1, wherein said implement is slidingly mounted to said device.
12. The device of claim 1, wherein said implement is rotatively mounted to said device.
13. The device of claim 1, wherein said abrasive end comprises a plurality of bristles.
14. The device of claim 1, wherein said vessel comprises a distal terminus formed into an unevenly shaped tip.
15. The device of claim 4, wherein said vessel comprises a distal terminus comprising a plug having an outlet aperture sized to allow passage of an amount of said smoke-simulating powder therethrough.
16. The device of claim 3, wherein said device further comprises said vessel having a side wall; and
said side wall being formed to have at least one port therethrough in communication with said first chamber.
17. The device of claim 16, wherein said insert comprises an inlet hole located to be in substantial alignment with said port.
18. The device of claim 16, wherein said abrasive end comprises a plurality of bristles, and wherein said at least one port is located to direct a flow of inhaled air through said bristles.
19. A simulated cigarette kit comprises:
a vessel defining a hollow interior;
first and second interchangeable inserts each being sized and shaped to be temporarily secured within said interior; and,
wherein said first insert is adapted to carry a first aromatic substance thereon, and said second insert is adapted to carry a second aromatic substance thereon.
20. The kit of claim 19, wherein said first and second substances have different flavored aromas.