US 6,284,865 B1Granted

Polymeric phosphite composition and hydrocyanation of unsaturated organic compounds and the isomerization of unsaturated nitriles

AssigneeE. I. Du Pont de Nemours and Company

InventorsWilson Tam, Sigridur Soley Kristjansdottir, Robin Nikolas Greene

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Abstract

A polymeric composition, a process for producing the composition, and a process for using the composition in, for example, hydrocyanation or isomerization are disclosed. The composition comprises repeat units derived from (1) a carbonyl compound, a monomer, and phosphorochloridite; (2) phosphorus trichloride, a polyhydric alcohol, and an aromatic diol; or (3) combinations of (1) and (2) in which the monomer can be a polyhydric alcohol, an amine, combinations thereof. The composition can further comprise a Group VIII metal and optionally a Lewis acid. The composition can be produced by (1) contacting a carbonyl compound with the monomer to produce an intermediate and contacting the intermediate with phosphorochloridite; (2) contacting phosphorus trichloride with a second polyhydric alcohol under a condition sufficient to produce a phosphorus-containing polymer and contacting the phosphorus-containing polymer with an aromatic diol; or (3) contacting an N,N-dialkyl dichlorophosphoramidite with a second polyhydric alcohol to produce a polymer phosphoramidite, contacting the polymer phosphoramidite with an acid such as HCl to produce the phosphorus-containing polymer, which is then contacted with an aromatic diol. The composition can be used as catalyst, for example, for converting an unsaturated organic compound to a nitrile and isomerizing a nitrile.

Claims22

Dependent claims

A polymeric composition comprising repeat units derived from (1) a carbonyl compound, (2) a monomer, and (3) phosphorochloridite wherein said carbonyl compound has the formula selected from the group consisting of (R1O2C)m (OH)—Ar1—(OH)(CO2R1)m, (R1O2C)m (OH)—Ar2—A2—Ar2—(OH)(CO2R1)m, (R1O2C)m (OH)—Ar2—Ar2—(OH)(CO2R1)m and combinations of two or more thereof;

said monomer is selected from the group consisting of polyhydric alcohols, amines, and combinations thereof,
said phosphorochloridite has the formula selected from the group consisting of ClP(O—Ar2—R2)2;
the Ar2 groups in ClP(O—Ar2—R2)2 are unlinked to each other, directly linked to each other, or linked to each other through group A2;
each Ar1 is selected from the group consisting of C6 to C40 phenylene group, C12 to C40 biphenylene group, C10 to C40 naphthylene group, C20 to C40 binaphthylene group, and combinations of two or more thereof;
each Ar2 is independently selected from the group consisting of C6 to C40 phenylene group, C10 to C40 naphthylene group, and combinations thereof;
A2 is selected from the group consisting of —C(R1)(R1), —O—, —N(R1)—, —S—, —S(O)2—, —S(O)—, and combinations of two or more thereof;
each R1 is independently selected from the group consisting of hydrogen, C1 to C12 alkyl group or cycloalkyl group, C6 to C20 aryl group, and combinations of two or more thereof;
each R2 is independently selected from the group consisting of hydrogen, C1 to C12 alkyl or cycloalkyl group, acetal, ketal, —OR3, —CO2R3, C6 to C20 aryl group, F, Cl, —NO2, —SO3R3, —CN, perhaloalkyl, —S(O)R3, —S(O)2R3, —CHO, —C(O)R3, cyclic ether, —A1Z, and combinations of two or more thereof;
A1 is a C1 to C12 alkylene group;
Z is selected from the group consisting of —CO2R3, —CHO, —C(O)R3, —C(O)SR3, —SR3, —C(O)NR1R1, —OC(O)R3, —OC(O)OR3, —N═C(R1)R1, —C(R1)═NR1, —C(R1)═N—O—R1, —P(O)(OR3)(OR3), —S(O)2R3, —S(O)R3, —C(O)OC(O)R3, —NR3CO2R3, —NR3C(O)N(R1)R1, F, Cl, —NO2, —SO3R3, —CN, and combinations of two or more thereof;
each R3 is independently selected from the group consisting of C1 to C12 alkyl or cycloalkyl group, C6 to C20 aryl group, and combinations thereof;
and
each m is independently a number in the range of from 1 to 2.

10 more elements

A process comprising (1) contacting a carbonyl compound with a monomer to produce an intermediate and (2) contacting said intermediate with a phosphorchloridite wherein

said carbonyl compound has the formula selected from the group consisting of (R1O2C)m(OH)—Ar1—(OH)(CO2R1)m, (R1O2C)m(OH)—Ar2—A2—Ar2—(OH)(CO2R1)m, (R1O2C)m(OH)—Ar2—Ar2—(OH)(CO2R1)m and combinations of two or more thereof;
said monomer is selected from the group consisting of polyhydric alcohols, amines, and combinations thereof;
said phosphorochloridite has the formula selected from the group consisting of ClP(O—Ar2—R2)2;
the Ar2 groups in ClP(O—Ar2—R2)2 are unlinked to each other, directly linked to each other, or linked to each other through group A2;
each Ar1 is selected from the group consisting of phenylene group, biphenylene group, naphthylene group, binaphthylene group, and combinations of two or more thereof;
each Ar2 is independently selected from the group consisting of phenylene group, naphthylene group, and combinations thereof;
A2 is selected from the group consisting of —C(R1)(R1)—, —O—, —N(R1)—, —S—, —S(O)2—, —S(O)—, and combinations of two or more thereof;
each R1 is independently selected from the group consisting of hydrogen, C1 to C12 alkyl or cycloalkyl group, C6 to C20 aryl group, and combinations of two or more thereof;
each R2 is independently selected from the group consisting of hydrogen, C1 to C12 alkyl or cycloalkyl group, acetal, ketal, —OR3, —CO2R3, C6 to C20 aryl group, F, Cl, —NO2, —SO3R3, —CN, perhaloalkyl, —S(O)R3, —S(O)2R3, —CHO, —C(O)R3, cyclic ether, —A1Z, and combinations of two or more thereof;
Z is selected from the group consisting of —CO2R3, —CHO, —C(O)R3, —C(O)SR3, —SR3, —C(O)NR1R1, —OC(O)R3, —OC(O)OR3, —N═C(R1)R1, —C(R1)═NR1, —C(R1)═N—O—R1, —P(O)(OR3)(OR3), —S(O)2R3, —S(O)R3, —C(O)OC(O)R3, —NR3CO2R3, —NR3C(O)N(R1)R1, F, Cl, —NO2, —SO3R3, —CN, and combinations of two or more thereof;
A1 is a C1 to C12 alkylene group;
each R3 is independently selected from the group consisting of C1 to C12 alkyl or cycloalkyl group, C6 to C20 aryl group, and combinations thereof;
and
each m is independently a number in the range of from 1 to 2.

11 more elements

Dependencies are inferred from the claim text.

Facts

Application: 09/399,261Filed 20 Sep 1999
Granted: 4 Sep 2001
Term ends: Not estimatedThe source records don’t support an estimate.

Classification16 codes

C08G 79/04
A linkage containing phosphorus: phosphorus linked to oxygen or to oxygen and carbon
B01J 31/06
Containing organic compounds or metal hydrides: containing polymers
B01J 31/1658
Polymer immobilised coordination complexes, e.g. organometallic complexes: immobilised by covalent linkages, i.e. pendant complexes with optional…
B01J 31/185
The ligands containing phosphorus: phosphites , their isomeric phosphonates and RO-substitution derivatives thereof