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公开(公告)号：JPH1036421A
公开(公告)日：1998-02-10
申请号：JP9239497
申请日：1997-04-10
Applicant: SHELL INT RESEARCH
Inventor： DE BOER ERIC JOHANNES MARIA , HESSEN BART , VAN DER HUIZEN ADRIAAN ALBERT , DE JONG WOUTER , VAN DER LINDEN ADRIANUS JOHANN , RUISCH BART JOHAN , SCHOON LODEWIJK , DE SMET HELEEN JOHANNA AUGUSTA , VAN DER STEEN FREDERIK HENDRIK , VAN STRIEN HUBERTUS CORNELIS T , VILLENA ALAN , WALHOF JUDITH JOHANNA BERENDIN
Abstract: PROBLEM TO BE SOLVED: To provide a catalyst which is more effective than a known catalysts, is stable, is active even when used in sufficiently low concentrations and is suitable for use in the hydrogenation of a polymer having ethylenic unsaturations by using a plurality of specified compounds. SOLUTION: This composition comprises a titanium compound represented by formula I, an alkali metal hydride which is initially added or produced in situ from an alkali-metal-terminated living polymer and/or an added alkyl alkali metal and hydrogen in the polymer solution, the molar ratio of the alkali metal to the titanium being at least 2:1, and a boron compound represented by formula II (wherein A1 and A2 are each cyclopentadienyl or indenyl; X1 and X2 are each H, a halogen, a lower alkyl, a lower alkoxyl or the like; and R1 , R2 and R3 are each a halogen, a lower alkyl, a lower alkoxyl or the like).
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公开(公告)号：JPH10101727A
公开(公告)日：1998-04-21
申请号：JP25562197
申请日：1997-09-19
Applicant: SHELL INT RESEARCH
Inventor： VAN DER HEIJDEN HARRY , HESSEN BART
Abstract: PROBLEM TO BE SOLVED: To enable hydrogenation of all types of olefins including a block polymer having a poly(conjugated diolefin) block with economy in respect of catalyst cost and time required for treating, by using a catalyst containing a specific metal compound cation and a non-coordinating stable anion. SOLUTION: This catalyst is obtained by combining (a) a metal cation of the formula [(A)(B)ML ] wherein M is Ti, Zr or Hf; and A and B are a ligand of formula I or II wherein R1 is a hydrocarbyl which may contain a heteroatom, R3 is R1 or a halogen, substituent R may be bonded commonly to A and B to form a bridge, m is 0 to 5, p is 0 to 4 and q is 0 to 3; and L is H or R1 ; with the proviso that when both of A and B are a ligand of formula I or formula II, at least one of m, p and q is 1 or more, and (b) a non-coordinating stable anion. 100g of an olefin containing an ethylenic unsaturated bond, an oligomer or a (co)polymer is hydrogenated in the presence of the above-mentioned catalyst composition in an amount of 0.1 to 0.75g in terms or group IV metal.
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公开(公告)号：JPH1053614A
公开(公告)日：1998-02-24
申请号：JP13678997
申请日：1997-05-27
Applicant: SHELL INT RESEARCH
Inventor： DE BOER ERIC JOHANNES MARIA , HESSEN BART , VAN DER HUIZEN ADRIAAN ALBERT , DE JONG WOUTER , VAN DER LINDEN ADRIANUS JOHANN , RUISCH BART JOHAN , SCHOON LODEWIJK , DE SMET HELEEN JOHANNA AUGUSTA , VAN DER STEEN FREDERIK HENDRIK , VAN STRIEN HUBERTUS CORNELIS T , VILLENA ALAN , WALHOF JUDITH JOHANNA BERENDIN
Abstract: PROBLEM TO BE SOLVED: To obtain a catalyst composition containing a titanium compound and an alkali metal compound, capable of exhibiting an excellent effect in a low concentration and capable of being effectively used for the hydrogenation of a polymer containing ethylenic unsaturated bonds. SOLUTION: This catalyst composition contains at least (A) a titanium compound of the formula (A1 is a heterocyclic five-membered ring containing a heteroatomic phosphorus or nitrogen; A2 is A1 , cyclopentadienyl, etc.; L1 , L2 are each H, a halogen, a lower alkyl, phenyl, etc.), and (B) an alkali metal hydride itself or the alkali metal hydride prepared from an alkali metal- terminated living polymer in the polymer solution in situ. The molar ratio of the alkali metal: titanium is preferably at least 2:1. The employment of the catalyst composition enables to hydrogenate an olefinic unsaturated polymer in a state dissolved in a hydrocarbon solvent, and also to hydrogenate the polymer after polymerized in a hydrocarbon solvent.
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4.发明专利
公开(公告)号：JPH1017607A
公开(公告)日：1998-01-20
申请号：JP5962797
申请日：1997-03-13
Applicant: SHELL INT RESEARCH
Inventor： DE BOER ERIC JOHANNES MARIA , HESSEN BART , VAN DER HUIZEN ADRIAAN ALBERT , DE JONG WOUTER , VAN DER LINDEN ADRIANUS JOHANN , RUISCH BART JOHAN , SCHOON LODEWIJK , DE SMET HELEEN JOHANNA AUGUSTA , VAN DER STEEN FREDERIK HENDRIK , VAN STRIEN HUBERTUS CORNELIS T , VILLENA ALAN , WALHOF JUDITH JOHANNA BERENDIN
IPC: C07F7/28 , B01J31/12 , B01J31/22 , C07C17/00 , C07F17/00 , C08C19/02 , C08F4/64 , C08F4/6592 , C08F8/04 , C08F36/04
Abstract: PROBLEM TO BE SOLVED: To obtain a catalyst compsn. which is useful for hydrogenating an ethylenially unsatd. polymer, is active at a sufficiently low concn., and it not required to be removed from the resultant hydrogenated polymer by incorporating a specific Ti compd. and a specific alkali metal hydride into the same. SOLUTION: This compsn. contains a Ti compd. represented by formula I wherein A1 is an indenyl group represented by formula II [wherein R1 and R2 are each a halogen, (substd.) phenyl, a lower alkyl, a (phenyl)alkoxy, phenoxy, benzyl, or a bulky group having at least one hetero atom (e.g. a tri- lower-alkylsilyl or -NPh2 ); n is 0-4; and m is 0-3]; A2 is A1 or (substd.) cyclopentadienyl; and L1 and L2 are each H, a halogen, a lower alkyl, phenyl, phenyloxy, etc.}, and an alkali metal hydride (e.g. lithium hydride) which is added as such or synthesized in situ in a polymer soln. from an alkyli-metal- terminated living polymer and/or an alkyli metal alkyl further added.
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公开(公告)号：DE69703855D1
公开(公告)日：2001-02-15
申请号：DE69703855
申请日：1997-03-14
Applicant: SHELL INT RESEARCH
Inventor： DE BOER ERIC JOHANNES MARIA , HESSEN BART , VAN DER HUIZEN ADRIAAN ALBERT , DE JONG WOUTER , VAN DER LINDEN ADRIANUS JOHANN , RUISCH BART JOHAN , SCHOON LODEWIJK , DE SMET HELEEN JOHANNA AUGUSTA , VAN DER STEEN FREDERIK HENDRIK , VAN STRIEN HUBERTUS CORNELIS T , VILLENA ALAN , WALHOF JUDITH JOHANNA BERENDIN
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Patent Agency Ranking
公开(公告)号：ES2153632T3
公开(公告)日：2001-03-01
申请号：ES97200774
申请日：1997-03-14
Applicant: SHELL INT RESEARCH
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公开(公告)号：DE69701169D1
公开(公告)日：2000-02-24
申请号：DE69701169
申请日：1997-05-28
Applicant: SHELL INT RESEARCH
Inventor： DE BOER ERIC JOHANNES MARIA , HESSEN BART , VAN DER HUIZEN ADRIAAN ALBERT , DE JONG WOUTER , VAN DER LINDEN ADRIANUS JOHANN , RUISCH BART JOHAN , SCHOON LODEWIJK , DE SMET HELEEN JOHANNA AUGUSTA , VAN DER STEEN FREDERIK HENDRIK , VAN STRIEN HUBERTUS CORNELIS T , VILLENA ALAN , WALHOF JUDITH JOHANNA BERENDIN
Abstract: The invention provides a catalyst composition suitable for hydrogenation of polymers containing ethylenical unsaturation which comprises at least: (a) a titanium compound of the formula wherein A1 represents an optionally substituted heterocyclic five membered ring comprising a phosphorous or nitrogen heteroatom, and A2 has the same meaning as A1 or alternatively represents an optionally substituted cyclopentadienyl group or indenyl group, and wherein L1 and L2 may be the same or different and each may be selected from hydrogen, halogen, lower alkyl, phenyl, aralkyl, having from 7 to 10 carbons, lower alkoxy group, phenyloxy, phenylalkoxy group having from 7 to 10 carbon atoms, carboxyl, carbonyl, a SIMILAR CH2P(Phenyl)2, -CH2 Si(lower alkyl)3 or SIMILAR P(phenyl)2 group; and (b) an alkalimetal hydride, added as such or prepared in situ in the polymer solution from the alkalimetal terminated living polymer and/or from additionally added alkalimetal alkyl; and process for hydrogenation of polymers containing ethylenical unsaturation.
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公开(公告)号：DE69700309T2
公开(公告)日：2000-01-27
申请号：DE69700309
申请日：1997-04-11
Applicant: SHELL INT RESEARCH
Inventor： DE BOER ERIC JOHANNES MARIA , HESSEN BART , VAN DER HUIZEN ADRIAAN ALBERT , DE JONG WOUTER , VAN DER LINDEN ADRIANUS JOHANN , RUISCH BART JOHAN , SCHOON LODEWIJK , DE SMET HELEEN JOHANNA AUGUSTA , VAN DER STEEN FREDERIK HENDRIK , VAN STRIEN HUBERTUS CORNELIS T , VILLENA ALAN , WALHOF JUDITH JOHANNA BERENDIN
Abstract: The invention provides a catalyst composition suitable for hydrogenation of polymers containing ethylenical unsaturation, which comprise at least: (a) a titanium compound of the formula, wherein A1 and A2 are the same or different and each represents a substituted or unsubstituted cyclopentadienyl or indenyl group, wherein X1 and X2 are the same or different and each represents hydrogen, halogen, a lower alkyl or lower alkoxy, optionally substituted phenyl or phenoxy, or aralkyl having from 7 to 10 carbon atoms or phenylalkoxy having from 7 to 10 carbon atoms, carboxyl, carbonyl, a &tilde& CH2P(Phenyl)2, -CH2 Si(lower alkyl)3 or &tilde& P(phenyl)2 group; (b) an alkalimetal hydride, added as such or prepared in situ in the polymer solution from the alkalimetal terminated living polymer and/or from additionally added alkalimetal alkyl and hydrogen, the molar ratio of the alkalimetal: titanium in the polymer solution during hydrogenation being at least 2:1; and (c) a borium compound B(R1)(R2)(R3) wherein the symbols R1, R2 and R3 may be the same or different and each may represent hydrogen, halogen, lower alkyl or lower alkoxy, or phenyl optionally substituted by up to five substituents selected from halogen and lower alkyl, or benzyl having an optionally substituted phenyl ring as specified hereinbefore or wherein two of the symbols R may form together a monocyclic or bicyclic system which on its own may carry one or more substituents; and process for hydrogenation of polymers containing ehylenic unsaturation using these catalyst compositions.
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公开(公告)号：DE69700309D1
公开(公告)日：1999-08-12
申请号：DE69700309
申请日：1997-04-11
Applicant: SHELL INT RESEARCH
Inventor： DE BOER ERIC JOHANNES MARIA , HESSEN BART , VAN DER HUIZEN ADRIAAN ALBERT , DE JONG WOUTER , VAN DER LINDEN ADRIANUS JOHANN , RUISCH BART JOHAN , SCHOON LODEWIJK , DE SMET HELEEN JOHANNA AUGUSTA , VAN DER STEEN FREDERIK HENDRIK , VAN STRIEN HUBERTUS CORNELIS T , VILLENA ALAN , WALHOF JUDITH JOHANNA BERENDIN
Abstract: The invention provides a catalyst composition suitable for hydrogenation of polymers containing ethylenical unsaturation, which comprise at least: (a) a titanium compound of the formula, wherein A1 and A2 are the same or different and each represents a substituted or unsubstituted cyclopentadienyl or indenyl group, wherein X1 and X2 are the same or different and each represents hydrogen, halogen, a lower alkyl or lower alkoxy, optionally substituted phenyl or phenoxy, or aralkyl having from 7 to 10 carbon atoms or phenylalkoxy having from 7 to 10 carbon atoms, carboxyl, carbonyl, a &tilde& CH2P(Phenyl)2, -CH2 Si(lower alkyl)3 or &tilde& P(phenyl)2 group; (b) an alkalimetal hydride, added as such or prepared in situ in the polymer solution from the alkalimetal terminated living polymer and/or from additionally added alkalimetal alkyl and hydrogen, the molar ratio of the alkalimetal: titanium in the polymer solution during hydrogenation being at least 2:1; and (c) a borium compound B(R1)(R2)(R3) wherein the symbols R1, R2 and R3 may be the same or different and each may represent hydrogen, halogen, lower alkyl or lower alkoxy, or phenyl optionally substituted by up to five substituents selected from halogen and lower alkyl, or benzyl having an optionally substituted phenyl ring as specified hereinbefore or wherein two of the symbols R may form together a monocyclic or bicyclic system which on its own may carry one or more substituents; and process for hydrogenation of polymers containing ehylenic unsaturation using these catalyst compositions.
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公开(公告)号：MX9701870A
公开(公告)日：1998-04-30
申请号：MX9701870
申请日：1997-03-12
Applicant: SHELL INT RESEARCH
Inventor： BOER ERIC JOHANNES MARIA DE , HESSEN BART , HUIZEN ADRIAAN ALBERT VAN DER , JONG WOUTER DE , LINDEN ADRIANUS JOHANNES VAN D , RUISCH BART JOHAN , SCHOON LODEWIJK , SMET HELEEN JOHANNA AUGUSTA DE , STEEN FREDERIK HENDRIK VAN DER
IPC: C07F7/28 , B01J31/12 , B01J31/22 , C07C17/00 , C07F17/00 , C08C19/02 , C08F4/64 , C08F4/6592 , C08F8/04 , C08F36/04
Abstract: La presente invencion proporciona una composicion catalizadora para la hidrogenacion de polímeros que contienen insaturacion etilénica los cuales comprenden al menos: (a) un compuesto de titanio de la formula (Ver Formula) en donde A1 representa un grupo indenilo opcionalmente substituido, de la formula (Ver Formula) en donde los substituyentes R1 y R2 pueden ser los mismos o diferentes y cada uno puede ser seleccionada a partir de halogeno, fenilo, el cual puede soportar opcionalmente uno o más substituyentes, iguales o diferentes, entre alquilo inferior, alcoxi, fenoxi, fenilalcoxi, bencilo y substituyentes voluminosos que contengan uno o más heteroátomos tales como bis(alquilo inferior)sililo, -NPhs, -NHPh, -BPh2 y -B(OPh)2, en donde n puede ser un numero de 0 a 4 y m puede ser un numero de 0 a 3, o en donde A2 tiene el mismo significado como A1 o representa alternativamente un grupo ciclopentadieno opcionalmente substituido, y en donde L1 y L2 pueden ser iguales o diferentes y cada uno se puede seleccionar a partir de hidrogeno, halogeno, alquilo inferior, fenilo, aralquilo, que tenga de 7 a 10 átomos de carbono, grupo alcoxi inferior, feniloxi, grupo fenilalcoxi que tenga de 7 a 10 átomos de carbono, carboxilo, carbonilo, un grupo de coordinacion B-dicetona, un grupo -CH2P(fenil)2, -CH2 Si (alquilo inferior)3 o -P(fenil)2; y (b) y un hidruro de metal alcalino, adicionado tal cual o preparado in situ en la solucion del polímero a partir del polímero viviente terminado en metal alcalino y/o a partir de la adicion adicional de un alquilo de metal alcalino; y un proceso para la hidrogenacion de polímeros que contienen insaturacion etilénica.
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