1. A catalyst system comprising:
an aluminum alkyl, alumoxane or combinations thereof;
a first catalyst precursor prepared by contacting compound (I) represented by the formula:
with an substituted aryl alcohol;
wherein
Z\u2014O is a support material, where O is oxygen and Z is Si, Ti, Al, Sn, Fe, Ga, Zr, B, Mg or Cr;
each X is, independently, nitrogen, oxygen phosphorous, or sulfur, provided that both X’s are not each oxygen;
each n is, independently, 1 or 2, provided the total of n=3;
each R is, independently, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, provided at least one R group is an aryl or substituted aryl group; and
a second catalyst precursor, wherein the second catalyst precursor is a metallocene compound.
2. The catalyst system of claim 1, wherein each X is N.
3. The catalyst system of claim 1, wherein each R is, independently, methyl, ethyl, propyl, butyl, isobutyl, hexyl, isohexyl, octyl, cyclohexyl, dodecyl, phenyl, substituted phenyl, naphthyl, substituted naphthyl, biphenyl, substituted biphenyl, diphenylether, substituted diphenylether, tolyl, substituted tolyl, benzophenone, substituted benzophenone, or a mixture thereof.
4. The catalyst system of claim 1, wherein each R is, independently, phenyl, substituted phenyl, naphthyl, or substituted naphthyl.
5. The catalyst system of claim 1, wherein the aryl alcohol is phenol or biphenol and the phenol or biphenol is substituted with one or more fluorine atoms.
6. The catalyst system of claim 5, wherein the substituted biphenol is \u2014OC6F4C6F5.
7. The catalyst system of claim 1, wherein the alkyl alcohol or aryl alcohol is present in a molar excess.
8. The catalyst system of claim 1, wherein the aluminum alkyl is represented by the formula Al(R\u2033)3, where each R\u2033 is, independently, a C1 to C30 alkyl group.
9. The catalyst system of claim 1, wherein the aluminum alkyl is trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, or tri-n-octylaluminum and mixtures thereof.
10. The catalyst system of claim 1, wherein the metallocene compound has the formula:
wherein:
M is the metal center, and is a Group 4 metal preferably titanium, zirconium or hafnium, preferably zirconium or hafnium;
A can be present or absent and when present is selected from R1R2Si, R1R2C, (R1R2C)2, (R1R2Si)2, CH2, CH2CH2, wherein R1 and R2 are independently selected from branched or unbranched C1 to C20 hydrocarbyl radicals, phenyl, and substituted phenyl, and when A is bridged, the catalyst represented can be a racemic or a meso form;
L1 and L2 are the same or different cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl rings, optionally substituted, that are each bonded to M, or L1 and L2 are the same or different cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl optionally substituted rings, in which any two adjacent R groups on the rings are optionally joined to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
X1 and X2 are, independently, hydrogen, halogen, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbyl radicals, or substituted germylcarbyl radicals; or both X are joined and bound to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms; or both together can be an olefin, diolefin or aryne ligand.
11. The catalyst system of claim 1, wherein the metallocene compound is Me2Si(H4Ind)2ZrMe2, Me2Si(1,3-Me,Bu-Cp)2ZrMe2, Me2Si(2-Me-Ind)2ZrMe2, Me2Si(2-Me-4-Ph-Ind)2Z-Me2 or mixtures thereof.
12. A catalyst system consisting essentially of:
an aluminum alkyl;
a first catalyst precursor prepared by contacting compound (I) represented by the formula:
with an substituted aryl alcohol;
wherein
Z\u20140 is a support material, where O is oxygen and Z is Si, Ti, Al, Sn, Fe, Ga, Zr, B, Mg or Cr;
each X is, independently, nitrogen, oxygen, phosphorous, or sulfur, provided that both X’s are not each oxygen;
each n is, independently, 1 or 2, provided the total of n=3;
each R is, independently, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, provided at least one R group is an aryl or substituted aryl group; and
a second catalyst precursor, wherein the second catalyst precursor is a metallocene compound having the formula:
wherein:
M is the metal center, and is a Group 4 metal preferably titanium, zirconium or hafnium, preferably zirconium or hafnium;
A can be present or absent and when present is selected from R1R2Si, R1R2C, (R1R2C)2, (R1R2Si2, CH2, CH2CH2, wherein R1 and R2 are independently selected from branched or unbranched C1 to C20 hydrocarbyl radicals, phenyl, and substituted phenyl, and when A is bridged, the catalyst represented can be a racemic or a meso form;
L1 and L2 are the same or different cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl rings, optionally substituted, that are each bonded to M, or L1 and L2 are the same or different cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl optionally substituted rings, in which any two adjacent R groups on the rings are optionally joined to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
X1 and X2 are, independently, hydrogen, halogen, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbyl radicals, or substituted germylcarbyl radicals; or both X are joined and bound to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms; or both together can be an olefin, diolefin or aryne ligand.
13. A process to polymerize monomers comprising contacting monomers with a catalyst system comprising:
an aluminum alkyl, alumoxane or combinations thereof;
a first catalyst precursor prepared by contacting compound (I) represented by the formula:
with substituted aryl alcohol;
wherein
Z\u2014O is a support material, where O is oxygen and Z is Si, Ti, Al, Sn, Fe, Ga, Zr, B, Mg or Cr;
each X is, independently, nitrogen, oxygen phosphorous, or sulfur, provided that both X’s are not each oxygen;
each n is, independently, 1 or 2, provided the total of n=3;
each R is, independently, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, provided at least one R group is an aryl or substituted aryl group; and
a second catalyst precursor, wherein the second catalyst precursor is a metallocene compound.
14. The process of claim 13, wherein the aryl alcohol is a phenol or a biphenol and the phenol or biphenol is substituted with one or more fluorine atoms.
15. The process of claim 13, wherein each X is N.
16. The process of claim 13, wherein the monomers comprise ethylene.
17. The process of claim 13, wherein the monomers comprise propylene.
18. The process of claim 14, wherein the monomers further comprise at least one comonomer selected from the group consisting of propylene, butene-1,4-methyl-pentene-1,3-methyl-pentene-1, hexene-1 and octene-1.
19. The process of claims 18, wherein the monomers further comprise a diene.
20. The process of claim 19, wherein the diene is selected from the group consisting of butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, and dicyclopentadiene.
21. The process of claim 19, wherein the diene is present at from 0.00001 to 1.0 weight %, based upon the total weight of the composition.
22. The process of claim 13, wherein the aluminum alkyl is represented by the formula Al(R\u2033)3, where each R\u2033 is, independently, a C1 to C30 alkyl group.
23. The process of claim 21, wherein each R\u2033 is, independently, selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, and all isomers thereof.
24. The process of claim 12, wherein the aluminum alkyl is selected from the group consisting of trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, or tri-n-octylaluminum and mixtures thereof.
25. The process of claim 13, wherein the metallocene compound has the formula:
wherein:
M is the metal center, and is a Group 4 metal preferably titanium, zirconium or hafnium, preferably zirconium or hafnium;
A can be present or absent and when present is selected from R1R2S, R1R2C, (R1R2C)2, (R1R2Si)2, CH2, CH2CH2, wherein R1 and R2 are independently selected from branched or unbranched C1 to C20 hydrocarbyl radicals, phenyl, and substituted phenyl, and when A is bridged, the catalyst represented can be a racemic or a meso form;
L1 and L2 are the same or different cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl rings, optionally substituted, that are each bonded to M, or L1 and L2 are the same or different cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl optionally substituted rings, in which any two adjacent R groups on the rings are optionally joined to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
X1 and X2 are, independently, hydrogen, halogen, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbyl radicals, or substituted germylcarbyl radicals; or both X are joined and bound to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms; or both together can be an olefin, diolefin or aryne ligand.
26. The process of claim 13, wherein the metallocene compound is Me2Si(H4Ind)2ZrMe2, Me2Si(1,3-Me,Bu-Cp)2ZrMe2, Me2Si(2-Me-Ind)2ZrMe2, Me2Si(2-Me-4-Ph-Ind)2Z-Me2 or mixtures thereof.
27. A process to polymerize monomers comprising contacting monomers with a catalyst system consisting essentially of:
an aluminum alkyl;
a first catalyst precursor prepared by contacting compound (I) represented by the formula:
with substituted aryl alcohol;
wherein
Z\u2014O is a support material, where O is oxygen and Z is Si, Ti, Al, Sn, Fe, Ga, Zr, B, Mg or Cr;
each X is, independently, nitrogen, oxygen phosphorous, or sulfur, provided that both X’s are not each oxygen;
each n is, independently, 1 or 2, provided the total of n=3;
each R is, independently, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, provided at least one R group is an aryl or substituted aryl group; and
a second catalyst precursor, wherein the second catalyst precursor is a metallocene compound having the formula:
wherein:
M is the metal center, and is a Group 4 metal preferably titanium, zirconium or hafnium, preferably zirconium or hafnium;
A can be present or absent and when present is selected from R1R2Si, R1R2C, (R1R2C)2, (R1R2Si)2, CH2, CH2CH2, wherein R1 and R2 are independently selected from branched or unbranched C1 to C20 hydrocarbyl radicals, phenyl, and substituted phenyl, and when A is bridged, the catalyst represented can be a racemic or a meso form;
L1 and L2 are the same or different cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl rings, optionally substituted, that are each bonded to M, or L1 and L2 are the same or different cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl optionally substituted rings, in which any two adjacent R groups on the rings are optionally joined to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
X1 and X2 are, independently, hydrogen, halogen, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbyl radicals, or substituted germylcarbyl radicals; or both X are joined and bound to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms; or both together can be an olefin, diolefin or aryne ligand.
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 information processing apparatus comprising:
an obtaining unit that obtains position information and time information, the position information indicating a position at which a writing action has been performed and which is specified in accordance with code information formed on a medium to which an operation result for operation items is input by the writing action, the time information indicating a time at which the writing action was performed;
a specifying unit that specifies, in accordance with the position information, an operation item for which the writing action has been performed;
a calculating unit that calculates, in accordance with the time information, an operation time taken to perform an operation of the operation item for which the writing action has been performed; and
an evaluating unit that detects an operation item in which a time difference between the operation time calculated by the calculating unit and a predetermined standard operation time taken to perform the operation of the operation item for which the writing action has been performed is longer than or equal to a predetermined time.
2. The information processing apparatus according to claim 1,
wherein the calculating unit calculates a time difference between an end time of a writing action for a first operation item and an end time of a writing action for a second operation item, the writing action for the second operation item being performed next to the writing action for the first operation item, the time difference being regarded as an operation time taken to perform an operation of the second operation item.
3. The information processing apparatus according to claim 1,
wherein, if the evaluating unit detects an operation item in which a time difference between the operation time calculated by the calculating unit and the standard operation time is longer than or equal to the predetermined time, the evaluating unit outputs a warning in accordance with a time difference between a total sum of operation times of all operation items for which the operation result has been input and a total sum of standard operation times of all the operation items.
4. The information processing apparatus according to claim 2,
wherein, if the evaluating unit detects an operation item in which a time difference between the operation time calculated by the calculating unit and the standard operation time is longer than or equal to the predetermined time, the evaluating unit outputs a warning in accordance with a time difference between a total sum of operation times of all operation items for which the operation result has been input and a total sum of standard operation times of all the operation items.
5. The information processing apparatus according to claim 1,
wherein the calculating unit further calculates, in accordance with the time information, an order in which operations of the individual operation items have been performed, and
wherein the evaluating unit further detects an operation item for which an operation has been performed in an order different from a predetermined standard operation order.
6. The information processing apparatus according to claim 2,
wherein the calculating unit further calculates, in accordance with the time information, an order in which operations of the individual operation items have been performed, and
wherein the evaluating unit further detects an operation item for which an operation has been performed in an order different from a predetermined standard operation order.
7. The information processing apparatus according to claim 3,
wherein the calculating unit further calculates, in accordance with the time information, an order in which operations of the individual operation items have been performed, and
wherein the evaluating unit further detects an operation item for which an operation has been performed in an order different from a predetermined standard operation order.
8. The information processing apparatus according to claim 4,
wherein the calculating unit further calculates, in accordance with the time information, an order in which operations of the individual operation items have been performed, and
wherein the evaluating unit further detects an operation item for which an operation has been performed in an order different from a predetermined standard operation order.
9. The information processing apparatus according to claim 1,
wherein the evaluating unit compares an operation result which has been input to a first medium provided to an operation target and which has been specified in accordance with the position information, with an operation result which has been input to a second medium different from the first medium and which has been specified in accordance with the position information, and outputs a comparison result.
10. The information processing apparatus according to claim 2,
wherein the evaluating unit compares an operation result which has been input to a first medium provided to an operation target and which has been specified in accordance with the position information, with an operation result which has been input to a second medium different from the first medium and which has been specified in accordance with the position information, and outputs a comparison result.
11. The information processing apparatus according to claim 3,
wherein the evaluating unit compares an operation result which has been input to a first medium provided to an operation target and which has been specified in accordance with the position information, with an operation result which has been input to a second medium different from the first medium and which has been specified in accordance with the position information, and outputs a comparison result.
12. The information processing apparatus according to claim 4,
wherein the evaluating unit compares an operation result which has been input to a first medium provided to an operation target and which has been specified in accordance with the position information, with an operation result which has been input to a second medium different from the first medium and which has been specified in accordance with the position information, and outputs a comparison result.
13. The information processing apparatus according to claim 5,
wherein the evaluating unit compares an operation result which has been input to a first medium provided to an operation target and which has been specified in accordance with the position information, with an operation result which has been input to a second medium different from the first medium and which has been specified in accordance with the position information, and outputs a comparison result.
14. The information processing apparatus according to claim 6,
wherein the evaluating unit compares an operation result which has been input to a first medium provided to an operation target and which has been specified in accordance with the position information, with an operation result which has been input to a second medium different from the first medium and which has been specified in accordance with the position information, and outputs a comparison result.
15. The information processing apparatus according to claim 7,
wherein the evaluating unit compares an operation result which has been input to a first medium provided to an operation target and which has been specified in accordance with the position information, with an operation result which has been input to a second medium different from the first medium and which has been specified in accordance with the position information, and outputs a comparison result.
16. An information processing method comprising:
obtaining position information and time information, the position information indicating a position at which a writing action has been performed and which is specified in accordance with code information formed on a medium to which an operation result for operation items is input by the writing action, the time information indicating a time at which the writing action was performed;
specifying, in accordance with the position information, an operation item for which the writing action has been performed;
calculating, in accordance with the time information, an operation time taken to perform an operation of the operation item for which the writing action has been performed; and
detecting an operation item in which a time difference between the operation time calculated by the calculating and a predetermined standard operation time taken to perform the operation of the operation item for which the writing action has been performed is longer than or equal to a predetermined time.
17. An information processing apparatus comprising:
a detecting unit that detects that a writing action has been performed on a medium;
a reading unit that reads position information on the medium when the detecting unit detects that a writing action has been performed on the medium;
an obtaining unit that obtains time information indicating a time at which the detecting unit detects that a writing action has been performed on the medium;
a memory that stores the position information and the time information in association with each other;
an operation item memory that stores operation items and pieces of position information in association with each other;
a time specifying unit that specifies first time information indicating a time at which a writing action was performed for a first operation item and second time information indicating a time at which a writing action was performed for a second operation item, by referring to the memory and the operation item memory, the first operation item and the second operation item being included in the operation items stored in the operation item memory, the first time information and the second time information being included in the time information obtained by the obtaining unit; and
a calculating unit that calculates a difference between the first time information and the second time information, the difference being regarded as an operation time of the first operation item.
18. The information processing apparatus according to claim 17, further comprising:
an evaluating unit that evaluates whether or not the operation time calculated by the calculating unit is longer than an operation time which is predetermined for the specified operation item.
19. The information processing apparatus according to claim 17,
wherein the time specifying unit specifies third time information indicating a time at which a writing action was performed for a third operation item, by referring to the memory and the operation item memory,
wherein the information processing apparatus further comprises an end time obtaining unit that obtains fourth time information indicating a time at which a writing action for the third operation item finished,
wherein the calculating unit calculates a difference between the second time information and the third time information, the difference being regarded as an operation time of the second operation item, and also calculates a difference between the third time information and the fourth time information, the difference being regarded as an operation time of the third operation item, and
wherein the information processing apparatus further comprises an evaluating unit that evaluates whether or not a total time of the operation times of the first operation item, the second operation item, and the third operation item is longer than a predetermined time.
20. The information processing apparatus according to claim 19, further comprising:
a warning unit that outputs a warning in accordance with how much the total time of the operation times of the first operation item, the second operation item, and the third operation item is longer than the predetermined time.