Phosphorus-containing compositions and their use in hydrocyanation, isomerization and hydroformylation reactions

A process for preparing compositions comprising phosphorus-containing, bidentate ligand (monomer) compounds of Formula I, wherein a is 1 or 2 and b is 0 or 1 with the condition that a+b=2, or compounds of Formula II, wherein a is 1 or 2 and b is 0 or 1 with the condition that a+b=2,

• 18
• wherein:
• x=0 to 4;
• y=0 to 2;
• each Ar is individually selected from the group consisting of phenyl, substituted phenyl, naphthyl, and substituted naphthyl, provided that the two Ar groups that are directly or indirectly bonded to the same phosphorus atom may be linked to each other by a linking unit selected from the group consisting of direct bond, alkylidene, secondary or tertiary amine, oxygen, sulfide, sulfone, and sulfoxide;
• each R″ is individually selected from the group consisting of hydrogen, linear or branched alkyl, cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine, chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarbylcarbonyl, cyclic ether, ethenyl, propenyl, and an organic radical with a terminal ethenyl or propenyl;
• each R is individually selected from the group consisting of hydrogen, acryloyl, methacryloyl and an organic radical with a terminal acryloyl, or methacryloyl group;
• provided at least one R is acryloyl or methacryloyl or an organic radical with a terminal acryloyl or methacryloyl group, said process comprising:
• (1) reacting at least one of acryloyl chloride or methacryloyl chloride with a polyhydric alcohol to make at least one of monoacrylate or monomethacrylate,
• (2) reacting at least one of monoacrylate or monomethacrylate with at least one of phosphorus trichloride or phosphorodichloridite or aryldichlorophosphine (Cl2P—Ar) to give at least one phosphorochloridite- or aryl,aryloxychlorophosphinite-containing acrylate or methacrylate,
• (3) reacting at least one phosphorochloridite- or aryl,aryloxychlorophosphinite-containing acrylate and/or methacrylate from step (2) with at least one compound of Formula III and/or at least one compound of Formula IV,
• 19
• wherein:
• each R′ individually is hydrogen or M, wherein M is an alkali metal or an alkaline earth metal.

A method for making a polymeric, phosphorus-containing composition by heating, in the presence of an initiator, and, optionally in the presence of a Group VIII transition metal, a composition comprising at least one compound of Formula I and/or at least one compound of Formula II,

• 20
• wherein:
• x=0 to 4;
• y=0 to 2;
• a and b are individually either 0, 1, or 2, provided a+b=2;
• each Ar is individually selected from the group consisting of phenyl, substituted phenyl, naphthyl, and substituted naphthyl, provided that the two Ar groups that are directly or indirectly bonded to the same phosphorus atom may be linked to each other by a linking unit selected from the group consisting of direct bond, alkylidene, secondary or tertiary amine, oxygen, sulfide, sulfone, and sulfoxide;
• each Ar can be further substituted with C1 to C20 branched or straight chain alkyl, C1 to C20 cycloalkyl, C6 to C20 aryl, acetal, ketal, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine, chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarbylcarbonyl or cyclic ether;
• each R is individually selected from the group consisting of hydrogen, ethenyl, propenyl, acryloyl, methacryloyl and an organic radical with a terminal ethenyl, propenyl, acryloyl, or methacryloyl group;
• each R″ is individually selected from the group consisting of hydrogen, linear or branched alkyl, cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine, chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarbylcarbonyl, cyclic ether, ethenyl, propenyl, and an organic radical with a terminal ethenyl or propenyl group;
• provided at least one R represents ethenyl, propenyl, acryloyl, methacryloyl or the organic radical with a terminal ethenyl, propenyl, acryloyl, or methacryloyl group or at least one R″ represents ethenyl, propenyl, or the organic radical with a terminal ethenyl or propenyl group,
• at atmospheric pressure and a temperature between 20° C. and 150° C. for 1 to 100 hours to produce the polymeric composition.

A method for making a polymeric composition by heating, in the presence of an initiator, a composition comprising at least one compound of Formula III or at least one compound of Formula IV:

• 21
• wherein:
• x=0 to 4;
• y=0 to 2;
• each R′ is individually selected from the group consisting of hydrogen or an alkali metal or an alkaline earth metal or a hydroxyl protective group selected from the group consisting of alkyl, alkoxyalkyl, carbonylalkyl, and a crown ether formed by taking both R′ groups together;
• each R″ is individually selected from the group consisting of hydrogen, linear or branched alkyl, cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine, chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarboylcarbonyl, cyclic ether, ethenyl, propenyl, and an organic radical with a terminal ethenyl or propenyl group;
• provided at least one R″ is ethenyl, propenyl, or the organic radical with a terminal ethenyl or propenyl group.

A process for making a polymeric, phosphorus-containing composition by:

• (1) heating, in the presence of an initiator, a composition comprising at least one compound of Formula III and/or at least one compound of Formula IV:
• 22
• wherein:
• x=0 to 4;
• y=0 to 2;
• each R′ is individually selected from the group consisting of hydrogen or an alkali metal or an alkaline earth metal or a hydroxyl protective group selected from the group consisting of alkyl, alkoxyalkyl, carbonylalkyl, and a crown ether formed by taking both R′ groups together;
• each R″ is individually selected from the group consisting of hydrogen, linear or branched alkyl, cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine, chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarboylcarbonyl, cyclic ether, ethenyl, propenyl, and an organic radical with a terminal ethenyl or propenyl group;
• provided at least one R″ is ethenyl, propenyl, or the organic radical with a terminal ethenyl or propenyl group and
• (2) if R′ is a hydroxyl protective group, converting R′ to H or an alkali metal or alkaline earth metal and,
• (3) phosphonylating the product of step (1) if R′ is other than a hydroxyl protective group, or the product of steps (1) and (2) if R′ is a hydroxyl protective group, with trivalent phosphorus of a diaryloxyphosphite unit, —P(—O—Ar)2, a diarylphosphine unit, —P(Ar)2, or an aryl,aryloxyphosphinite unit, —P(Ar)(—O—Ar), or mixture thereof, where each Ar is individually selected from the group consisting of phenyl, substituted phenyl, naphthyl, and substituted naphthyl, provided that the two Ar groups that are directly or indirectly bonded to the same phosphorus atom may be linked to each other by a linking unit selected from the group consisting of direct bond, alkylidene, secondary or tertiary amine, oxygen, sulfide, sulfone, and sulfoxide.

A method to produce a polymeric, phosphorus-containing composition by heating a phosphorochloridite containing at least one acrylate or methyl acrylate group in the presence of an initiator to produce a polymer containing phosphorochloridite, and further reacting this polymer with a composition comprising at least one compound of Formula III and/or Formula IV:

• 23
• wherein:
• x=0 to 4;
• y=0 to 2;
• each R′ is individually selected from the group consisting of hydrogen or an alkali metal or an alkaline earth metal or a hydroxyl protective group selected from the group consisting of alkyl, alkoxyalkyl, carbonylalkyl, and a crown ether formed by taking both R′ groups together, with the provision that if R′ is protected, the protecting group must be removed before reacting the compound of Formula III and/or Formula IV with the polymer containing phosphorochloridite;
• each R″ is individually selected from the group consisting of hydrogen, linear or branched alkyl, cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine, chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarboylcarbonyl, cyclic ether, ethenyl, propenyl, and an organic radical with a terminal ethenyl or propenyl group;
• provided at least one R″ is ethenyl, propenyl, or the organic radical with a terminal ethenyl or propenyl group.