US2006264320A1PendingUtilityA1
Hydrophobization and silica for supported catalyst
Est. expiryJan 16, 2024(expired)· nominal 20-yr term from priority
C08F 110/06Y10T428/31678C08F 4/65927
51
PatentIndex Score
0
Cited by
0
References
0
Claims
Abstract
This invention relates to a catalyst support comprising the result of the combination of: (a) a support comprising hydroxyl groups; (b) a capping agent comprising a boron containing Lewis acid; and (c) an ionic activator, wherein at least some of the capping agent does not form a support bound activator.
Claims
exact text as granted — not AI-modified1 - 17 . (canceled)
18 . A catalyst system comprising a catalyst support and a catalyst, the catalyst support comprising the result of the combination of:
(a) a support comprising hydroxyl groups; (b) a capping agent comprising a boron containing Lewis acid; and (c) an ionic activator, wherein at least some of the capping agent does not form a support bound activator.
19 . The catalyst system of claim 18 , wherein the catalyst comprises a metallocene.
20 . The catalyst system of claim 18 , wherein the catalyst comprises:
cyclopentadienyltitaniumtrimethyl, cyclopentadienyltitaniumtriethyl, cyclopentadienyltitaniumtriisopropyl, cyclopentadienyltitaniumtriphenyl, cyclopentadienyltitaniumtribenzyl, cyclopentadienyltitanium-2,4-pentadienyl, cyclopentadienyltitaniumdimethylmethoxide, cyclopentadienyltitaniumdimethylchloride, pentamethylcyclopentadienyltitaniumtrimethyl, indenyltitaniumtrimethyl, indenyltitaniumtriethyl, indenyltitaniumtripropyl, indenyltitaniumtriphenyl, tetrahydroindenyltitaniumtribenzyl, pentamethylcyclopentadienyltitaniumtriisopropyl, pentamethylcyclopentadienyltitaniumtribenzyl, pentamethylcyclopentadienyltitaniumdimethylmethoxide, pentamethylcyclopentadienyltitaniumdimethylchloride, η 5 -2,4-dimethyl-1,3-pentadienyl)titaniumtrimethyl, octahydrofluorenyltitaniumtrimethyl, tetrahydroindenyltitaniumtrimethyl, etrahydrofluorenyltitaniumtrimethyl, (1,1-dimethyl-2,3,4,9,10-.eta.-1,4,5,6,7,8-hexahydronaphthalenyl)titaniumtrimethyl, (1,1,2,3-tetramethyl-2,3,4,9,10-,.eta.-1,4,5,6,7,8-hexahydronaphthalenyl)titaniumtrimethyl, (tert-butylamido)(tetramethyl-η5-cyclopentadienyl)dimethylsilanetitaniumdichloride, (tert-butylamido)(tetramethyl-η5-cyclopentadienyl)dimethylsilanetitaniumdimethyl, (tert-butylamido)(tetramethyl-η5-cyclopentadienyl)-1,2-ethanediyltitaniumdimethyl, (tert-butylamido)(tetramethyl-η5-indenyl)dimethylsilaLnetitaniumdimethyl, (tert-butylamido)(tetramethyl-η5-cyclopentadienyl)dimethylsilane titanium(III)2-(dimethylamino)benzyl; (tert-butylamido)(tetramethyl-η5-cyclopentadienyl)dimethylsilanetitanium(III)allyl, (tert-butylamido)(tetramethyl-η5-cyclopentadienyl)dimethylsilanetitanium(II)1,4-diphenyl-1,3-butadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(II)1,4-diphenyl-1,3-butadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV)1,3-butadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(II)1,4diphenyl-1,3-butadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV)1,3-butadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(II)1,3-pentadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(II)1,3-pentadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV)dimethyl, (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II)1,4-diphenyl-1,3-butadiene, (tert-butylamido)(tetramethyl-η5-cyclopentadienyl)dimethylsilanetitanium(IV)1,3-butadiene, (tert-butylamido)(tetramethyl-η5-cyclopentadienyl)dimethylsilanetitanium(II)1,4-dibenzyl-1,3-butadiene, (tert-butylamido)(tetramethyl-η5-cyclopentadienyl)dimethylsilanetitanium(II)2,4-hexadiene, (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II)3-methyl-1,3-pentadiene, (tert-butylamido)(2,4-dimethyl-1,3-pentadien-2-yl)dimethylsilanetitaniumdimethyl, (tert-butylamido)(1,1-dimethyl-2,3,4,9,10-.eta.-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl, (tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-.PI.-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl, biscyclopentadienylzirconiumdimethyl, biscyclopentadienyltitaniumdiethyl, cyclopentadienyltitaniumdiisopropyl, biscyclopentadienyltitaniumdiphenyl, biscyclopentadienylzirconiumdibenzyl, biscyclopentadienyltitanium-2,4-pentadienyl, biscyclopentadienyltitaniummethylmethoxide, biscyclopentadienyltitaniummethylchloride, bispentamethylcyclopentadienyltitaniumdimethyl, bisindenyltitaniumdimethyl, indenylfluorenyltitaniumdiethyl, bisindenyltitaniummethyl(2-(dimethylamino)benzyl), bisindenyltitaniummethyltrimethylsilyl, bistetrahydroindenyltitaniummethyltrimethylsilyl, bispentamethylcyclopentadienyltitaniumdiisopropyl, bispentamethylcyclopentadienyltitaniumdibenzyl, bispentamethylcyclopentadienyltitaniummethylmethoxide, bispentamethylcyclopentadienyltitaniummethylchloride, (dimethylsilyl-bis-cyclopentadienyl)zirconiumdimethyl, (dimethylsilyl-bis-pentamethylcyclopentadienyl)titanium-2,4-pentadienyl, (dimethylsilyl-bis-t-butylcyclopentadienyl)zirconiumdichloride, (methylene-bis-pentamethylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl, (dimethylsilyl-bis-indenyl)zirconiumdichloride, (dimethylsilyl-bis-2-methylindenyl)zirconiumdimethyl, (dimethylsilyl-bis-2-methyl-4-phenylindenyl)zirconiumdimethyl, (dimethylsilyl-bis-2-methylindenyl)zirconium-1,4-diphenyl-1,3-butadiene, (dimethylsilyl-bis-2-methyl-4-phenylindenyl)zirconium(II)1,4-diphenyl-1,3-butadiene, dimethylsilyl-bis-tetrahydroindenyl)zirconium(II)1,4-diphenyl-1,3-butadiene, (dimethylsilyl-bis-fluorenyl)zirconiumdichloride, (dimethylsilyl-bis-tetrahydrofluorenyl)zirconiumdi(trimethylsilyl), (isopropylidene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyl, (dimethylsilylpentamethylcyclopentadienylfluorenyl)zirconiumdimethyl, or a combination thereof.
21 . The catalyst system of claim 18 , wherein the catalyst comprises:
(tert-butylamido)(tetramethyl-η5-cyclopentadienyl)-1,2-ethanediylzirconiumdimethyl, (tert-butylamido)(tetramethyl-η5-cyclopentadienyl)-1,2-ethanediyltitaniumdimethylbenzyl, (methylamido)(tetramethyl-η5-cyclopentadienyl)-1,2-ethanediylzirconiumdibenzhydryl, (methylamido)(tetramethyl-η5-cyclopentadienyl)-1,2-ethanediyltitaniumdineopentyl, (ethylamido)(tetramethyl-η5-cyclopentadienyl)-methylenetitaniumdiphenyl, (tert-butylamido)dibenzyl(tetramethyl-η5-cyclopentadienyl)silanezirconiumdibenzyl, (benzylamido)dimethyl(tetramethyl-η5-cyclopentadienyl)silanetitaniumdi(trimethylsilyl), (phenylphosphido)dimethyl(tetramethyl-η5-cyclopentadienyl)silanezirconiumdibenzyl, or a combination thereof.
22 . The catalyst system of claim 18 , wherein the support comprises a plurality of particles, each particle having a plurality of pores arranged within the particle such that a surface of the pores defines an inner surface of the particle located internal to an outer surface of the particle, and wherein a concentration of the catalyst disposed on the inner surface of the particle is greater than a concentration of the catalyst disposed on the outer surface of the particle.
23 . The catalyst system of claim 18 , wherein the support comprising hydroxyl groups comprises silica.
24 . The catalyst system of claim 18 , wherein the support comprising hydroxyl groups comprises silica calcined at about 400° C. to about 700° C. for a time less than or equal to about 12 hours.
25 . The catalyst system of claim 18 , wherein the support comprising hydroxyl groups comprises silica calcined in the presence of a fluorine source.
26 . The catalyst system of claim 18 , wherein the fluorine source comprises a fluoride salt.
27 . The catalyst system of claim 18 , wherein the support comprises less then or equal to about 0.1 millimole Si—OH functional groups per gram of support.
28 . The catalyst system of claim 18 , wherein the support comprises less then or equal to about 0.05 millimoles Si—OH functional groups per gram of support.
29 . The catalyst system of claim 18 , wherein the support comprises less then or equal to about 0.001 millimoles Si—OH functional groups per gram of support.
30 . The catalyst system of claim 18 , wherein the support comprises a plurality of particles, each particle having a plurality of pores arranged within the particle such that a surface of the pores defines an inner surface of the particle located internal to an outer surface of the particle, and wherein a concentration of Si—OH functional groups disposed on the inner surface of the particle is greater than a concentration of Si—OH functional groups disposed on the outer surface of the particle.
31 . The catalyst system of claim 18 , wherein the capping agent comprises R 1 R 2 BH, and wherein R 1 and R 2 are independently at each occurrence an organic radical comprising: C 1 -C 40 -alkyl, C 1 -C 40 -haloalkyl, C 6 -C 40 -aryl, C 6 -C 40 -haloaryl, C 7 -C 40 -arylalkyl, C 7 -C 40 -halo-arylalkyl, or a combination comprising at least one of the foregoing.
32 . The catalyst system of claim 31 , wherein R 1 and R 2 are independently at each occurrence an organic radical comprising:
pentafluorophenyl, nonafluoroanthracenyl, undecafluorotetrahydronaphthyl, nonafluorofluorenyl, 2,3,4,6-tetrafluorophenyl, 2,3,5,6-tetrafluorophenyl, 2,3,5-trifluorophenyl, 2,4,6-trifluorophenyl, 1,3-difluorophenyl, 2,3,5,6-tetrafluoro-4-methylphenyl, 2,3,4,6-tetrafluoro-5-methylphenyl, 2,4,5-trifluoro-6-methylphenyl, 2,3,6-trifluoro-4-methylphenyl, 2,4,6-trifluoro-3-methylphenyl, 2,6-difluoro-3-methylphenyl, 2,4-difluoro-5-methylphenyl, 3,5-difluoro-2-methylphenyl, 4-methoxy-2,3,5,6-tetrafluorophenyl, 3-methoxy-2,4,5,6-tetrafluorophenyl, 2-methoxy-3,5,6-trifluorophenyl, 3-methoxy-2,5,6-trifluorophenyl, 3-methoxy-2,4,6-trifluorophenyl, 2-methoxy-3,5-difluorophenyl, 3-methoxy-2,6-difluorophenyl, 3-methoxy-4,6-difluorophenyl, 2-methoxy-4,6-difluorophenyl, 4-methoxy-2,6-difluorophenyl, or a combination comprising at least one of the foregoing.
33 . The catalyst system of claim 18 , wherein the capping agent comprises bis(perfluorophenyl)borane.
34 . The catalyst system of claim 18 , wherein the ionic activator comprises boron.
35 . The catalyst system of claim 33 , wherein the ionic activator comprises an ammonium salt.
36 . The catalyst system of claim 18 , wherein the ionic activator comprises:
trimethylammoniumtetraphenylborate, triethylammoniumtetraphenylborate, tripropylammoniumtetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, tri(t-butyl)ammoniumtetraphenylborate, N,N-dimethylaniliniumtetraphenylborate, N,N-diethylaniliniumtetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, trimethylammoniumtetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenylborate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, dicyclohexylammoniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, or a combination comprising at least one of the foregoing activators.
37 . The catalyst system of claim 18 , wherein the ionic activator comprises N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, or a combination comprising at least one of the foregoing.
38 . The catalyst system of claim 18 , wherein essentially all of the capping agent does not form a support bound activator.
39 . An addition polymerization process, wherein one or more addition polymerizable monomers are contacted with the catalyst system of claim 18 under addition polymerization conditions.
40 . The addition polymerization process of claim 39 , wherein the polymerizable monomer includes C 2 -C 100 olefins, C 2 -C 100 alpha olefins, or a combination comprising at least one of the foregoing.
41 . The addition polymerization process of claim 39 , carried out under slurry polymerization conditions.
42 . The addition polymerization process of claim 39 , carried out under gas phase polymerization conditions.
43 . The addition polymerization process of claim 39 , wherein condensed monomer or an inert diluent is present.
44 . A process to make a catalyst support comprising:
contacting a support material comprising hydroxyl groups with a capping agent comprising a boron containing Lewis acid to produce a capped silica; and contacting the capped silica with an activator to produce the catalyst support, wherein the capping agent comprises boron, and wherein at least some of the capping agent does not form a support bound activator.
45 . The process of claim 44 , wherein the capping agent comprises R 1 R 2 BH, and wherein R 1 and R 2 are independently at each occurrence an organic radical comprising: C 1 -C 40 -alkyl, C 1 -C 40 -haloalkyl, C 6 -C 40 -aryl, C 6 -C 40 -haloaryl, C 7 -C 40 -arylalkyl, C 7 -C 40 -halo-arylalkyl, or a combination comprising at least one of the foregoing.
46 . The process of claim 45 , wherein R 1 and R 2 are independently at each occurrence an organic radical comprising pentafluorophenyl, nonafluoroanthracenyl, undecafluorotetrahydronaphthyl, nonafluorofluorenyl, 2,3,4,6-tetrafluorophenyl, 2,3,5,6-tetrafluorophenyl, 2,3,5-trifluorophenyl, 2,4,6-trifluorophenyl, 1,3-difluorophenyl, 2,3,5,6-tetrafluoro-4-methylphenyl, 2,3,4,6-tetrafluoro-5-methylphenyl, 2,4,5-trifluoro-6-methylphenyl, 2,3,6-trifluoro-4-methylphenyl, 2,4,6-trifluoro-3-methylphenyl, 2,6-difluoro-3-methylphenyl, 2,4-difluoro-5-methylphenyl, 3,5-difluoro-2-methylphenyl, 4-methoxy-2,3,5,6-tetrafluorophenyl, 3-methoxy-2,4,5,6-tetrafluorophenyl, 2-methoxy-3,5,6-trifluorophenyl, 3-methoxy-2,5,6-trifluorophenyl, 3-methoxy-2,4,6-trifluorophenyl, 2-methoxy-3,5-difluorophenyl, 3-methoxy-2,6-difluorophenyl, 3-methoxy-4,6-difluorophenyl, 2-methoxy-4,6-difluorophenyl, 4-methoxy-2,6-difluorophenyl, or a combination comprising at least one of the foregoing.
47 . The process of claim 44 , wherein the capping agent comprises bis(perfluorophenyl)borane.
48 . The process of claim 44 , further comprising contacting the catalyst support with a catalyst precursor to produce a catalytic system.
49 . The process of claim 48 , wherein the catalyst precursor comprises a metallocene.
50 . A catalyst support comprising the result of the combination of:
(a) a support comprising hydroxyl groups; (b) a capping agent comprising a boron containing Lewis acid; and (c) an ionic activator, wherein at least some of the capping agent does not form a support bound activator as determined by:
I) performing a time resolved luminescence analysis on a reference analyte comprising a catalyst precursor that is not in combination with the activator, to produce a plurality of reference output values, each being associated with a time resolved emission intensity at an emission energy;
II) performing a time resolved luminescence analysis on a sample analyte comprising the catalyst precursor in combination with the catalyst support, to produce a plurality of sample output values, each being associated with a time resolved emission intensity at an emission energy;
III) determining a reference emission energy and a reference lifetime each associated with a maximum emission intensity in the reference output values;
IV) determining a plurality of sample emission energy values and a plurality of sample lifetime values, each associated with a maximum emission intensity in the sample output values;
V) subtracting each of the sample emission energy values from the reference emission energy to produce a plurality of energy difference values;
VI) subtracting each of the sample lifetime values from the reference lifetime to produce a plurality of lifetime difference values;
VII) determining that an energy difference value, a lifetime difference value, or both representative of the combination of the support comprising hydroxyl groups and the capping agent comprising a boron containing Lewis acid are essentially zero values, and determining that an energy difference value, a lifetime difference value, or both representative of the combination of the support comprising hydroxyl groups and the ionic activator are essentially non-zero values, to determine that at least some of the capping agent does not form a support bound activator.
51 . The catalyst support of claim 50 , wherein the capping agent comprises R 1 R 2 BH, and wherein R 1 and R 2 are independently at each occurrence an organic radical comprising: C 1 -C 40 -alkyl, C 1 -C 40 -haloalkyl, C 6 -C 40 -aryl, C 6 -C 40 -haloaryl, C 7 -C 40 -arylalkyl, C 7 -C 40 -halo-arylalkyl, or a combination comprising at least one of the foregoing.
52 . The catalyst support of claim 51 , wherein R 1 and R 2 are independently at each occurrence an organic radical comprising pentafluorophenyl, nonafluoroanthracenyl, undecafluorotetrahydronaphthyl, nonafluorofluorenyl, 2,3,4,6-tetrafluorophenyl, 2,3,5,6-tetrafluorophenyl, 2,3,5-trifluorophenyl, 2,4,6-trifluorophenyl, 1,3-difluorophenyl, 2,3,5,6-tetrafluoro-4-methylphenyl, 2,3,4,6-tetrafluoro-5-methylphenyl, 2,4,5-trifluoro-6-methylphenyl, 2,3,6-trifluoro-4-methylphenyl, 2,4,6-trifluoro-3-methylphenyl, 2,6-difluoro-3-methylphenyl, 2,4-difluoro-5-methylphenyl, 3,5-difluoro-2-methylphenyl, 4-methoxy-2,3,5,6-tetrafluorophenyl, 3-methoxy-2,4,5,6-tetrafluorophenyl, 2-methoxy-3,5,6-trifluorophenyl, 3-methoxy-2,5,6-trifluorophenyl, 3-methoxy-2,4,6-trifluorophenyl, 2-methoxy-3,5-difluorophenyl, 3-methoxy-2,6-difluorophenyl, 3-methoxy-4,6-difluorophenyl, 2-methoxy-4,6-difluorophenyl, 4-methoxy-2,6-difluorophenyl, or a combination comprising at least one of the foregoing.
53 . The catalyst support of claim 50 , wherein the capping agent comprises bis(perfluorophenyl)borane.
54 . The catalyst support of claim 50 , wherein the ionic activator comprises boron.
55 . The catalyst support of claim 54 , wherein the ionic activator comprises an ammonium salt.
56 . The catalyst support of claim 50 , wherein the ionic activator comprises:
trimethylammoniumtetraphenylborate, triethylammoniumtetraphenylborate, tripropylammoniumtetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, tri(t-butyl)ammoniumtetraphenylborate, N,N-dimethylaniliniumtetraphenylborate, N,N-diethylaniliniumtetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, trimethylammoniumtetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenylborate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate; di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, dicyclohexylammoniumtetrakis(pentafluorophenyl)borate triphenylphosphoniumtetrakis(pentafluorophenyl)borate, tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, or a combination comprising at least one of the foregoing activators.
57 . The catalyst support of claim 50 , wherein the ionic activator comprises N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, or a combination comprising at least one of the foregoing.
58 . The catalyst support of claim 50 , wherein essentially all of the capping agent does not form a support bound activator.Cited by (0)
No later patents cite this yet.
References (0)
No backward citations on record.