Methacrylate and acrylate polymers and processes for making same

A polymer produced by polymerizing a monomer selected from the group consisting of esters, amides, and nitrites of acrylic and methacrylic acid, and mixtures thereof, with a protected functional organometallic initiator of the formula

• M-Rn-Z-J-[A(R1R2R3)]x (III)
• wherein:
• M is an alkali metal;
• R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof;
• n is an integer from 0 to 5;
• Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups;
• J is oxygen, sulfur, or nitrogen;
• A is an element selected from Group IVa of the Periodic Table of Elements;
• R1, R2, and R3 are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms;
• and
• x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, to form a mono-protected, mono-functionalized living polymer, followed by quenching or functionalizing the living polymer with a functionalizing group capable of terminating and end-capping said living polymer.

A multi-branched or star-shaped polar polymer having at least one functional end produced by polymerizing a polar monomer selected from group consisting of esters, amides, and nitriles of acrylic and methacrylic acid, singly, sequentially, or as a mixture thereof, with a protected functional organometallic initiator having the formula:

• M-Rn-Z-J-[A(R1R2R3)]x (III)
• wherein:
• M is an alkali metal;
• R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof;
• n is an integer from 0 to 5;
• Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups;
• J is oxygen, sulfur, or nitrogen;
• A is an element selected from Group IVa of the Periodic Table of Elements;
• R1, R2, and R3 are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms;
• and
• x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, to form a mono-protected, mono-functionalized living polymer;
• and
• coupling said living polymer with at least one other living polymer with a linking agent.

A process for preparing polar polymers, comprising:

• polymerizing a polar monomer selected from the group consisting of esters, amides, and nitrites of acrylic and methacrylic acid, and mixtures thereof, with a protected functional organometallic initiator of the formula
• M-Rn-Z-J-[A(R1R2R3)]x (III)
• wherein:
• M is an alkali metal;
• R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof;
• n is an integer from 0 to 5;
• Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups;
• J is oxygen, sulfur, or nitrogen;
• [A(R1R2R3)]x is a protecting group in which:
• A is an element selected from Group IVa of the Periodic Table of Elements;
• R1, R2, and R3 are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms;
• and
• x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, to form a mono-protected, mono-functionalized living polymer.

A polymer having the formula:

• X′-FG-(Q)d-Rn-Z-J-X
• wherein:
• FG is a protected or non-protected functional group;
• Q is a polar hydrocarbyl group derived by incorporation of a polar monomer selected from group consisting of esters, amides, and nitrites of acrylic and methacrylic acid, and mixtures thereof;
• d is an integer from 10 to 2000;
• R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof;
• n is an integer from 0 to 5;
• Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups;
• J is oxygen, sulfur, or nitrogen;
• X is a polymer segment derived by incorporation of a comonomer reacted with J;
• and
• X′ is a polymer segment derived by incorporation of a comonomer reacted with FG,
• with the proviso that X′-FG and X-J are not the same.

A heterotelechelic polymer having the formula:

• FG-(Q)d-Rn-Z-J-[A(R1R2R 3)]x
• wherein:
• FG is a protected or non-protected functional group;
• Q is a polar hydrocarbyl group derived by incorporation of a polar monomer selected from group consisting of esters, amides, and nitrites of acrylic and methacrylic acid, and mixtures thereof;
• d is an integer from 10 to 2000;
• R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof;
• n is an integer from 0 to 5;
• Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups;
• and
• J is oxygen, sulfur, or nitrogen;
• [A(R1R2R3)]x is a protecting group, in which A is an element selected from Group IVa of the Periodic Table of Elements;
• R1, R2, and R3 are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms;
• and
• x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen,
• with the proviso that J-[A(R1R2R3)]x and FG are not the same.

A process for preparing a heterotelechelic polymer, comprising:

• polymerizing a polar monomer selected from the group consisting of esters, amides, and nitrites of acrylic and methacrylic acid, and mixtures thereof, with a protected functional organometallic initiator of the formula
• M-Rn-Z-J-[A (R1R2R3)]x
• wherein:
• M is an alkali metal;
• R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof;
• n is an integer from 0 to 5;
• Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups;
• J is oxygen, sulfur, or nitrogen;
• [A(R1R2R3)]x is a protecting group in which:
• A is an element selected from Group IVa of the Periodic Table of Elements;
• R1, R2, and R3 are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms;
• and
• x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, to form a mono-protected, mono-functionalized living polymer;
• and
• functionalizing said living polymer with a functionalizing agent to provide a heterotelechelic polymer having the formula:
• FG-(Q)d-Rn-Z-J-[A(R1R2R3)]x
• wherein:
• FG is a protected or non-protected functional group;
• Q is a polar hydrocarbyl group derived by incorporation of a polar monomer selected from group consisting of esters, amides, and nitriles of acrylic and methacrylic acid, and mixtures thereof;
• d is an integer from 10 to 2000;
• and
• R, n, Z, J, A, R1, R2, R3, and x have the meanings ascribed above;
• with the proviso that J-[A(R1R2R3)]x and FG are not the same.

A polymer produced by polymerizing a monomer selected from the group consisting of esters, amides, and nitrites of acrylic and methacrylic acid, and mixtures thereof, in a hydrocarbon solvent, with a protected functional organometallic initiator of the formula

• M-Rn-Z-J-[A(R1R2R3)]x
• wherein:
• M is an alkali metal;
• R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof;
• n is an integer from 0 to 5;
• Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups;
• J is oxygen, sulfur, or nitrogen;
• [A(R1R2R3)]x is a protecting group in which:
• A is an element selected from Group IVa of the Periodic Table of Elements;
• R1, R2, and R3 are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms;
• and
• x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, to form a mono-protected, mono-functionalized living polymer;
• quenching or functionalizing the living end of said living polymer;
• and
• subjecting said polymer to conditions sufficient to remove the protecting group [A(R1R2R3)]x.

A process for preparing polar polymers, comprising:

• polymerizing a polar monomer selected from the group consisting of esters, amides, and nitrites of acrylic and methacrylic acid, and mixtures thereof, in a hydrocarbon solvent, with a protected functional organometallic initiator of the formula
• M-Rn-Z-J-[A(R1R2R3)]x
• wherein:
• M is an alkali metal;
• R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof;
• n is an integer from 0 to 5;
• Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups;
• J is oxygen, sulfur, or nitrogen;
• [A(R1R2R3)]x is a protecting group in which:
• A is an element selected from Group IVa of the Periodic Table of Elements;
• R1, R2, and R3 are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms;
• and
• x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, to form a mono-protected, mono-functionalized living polymer;
• and
• deprotecting said polymer.

A multi-branched or star-shaped polar polymer having at least one functional end produced by polymerizing a polar monomer selected from group consisting of esters, amides, and nitriles of acrylic and methacrylic acid, singly, sequentially, or as a mixture thereof, in a hydrocarbon solvent, with a protected functional organometallic initiator having the formula:

• M-Rn-Z-J-[A(R1R2R3)]x
• wherein:
• M is an alkali metal;
• R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof;
• n is an integer from 0 to 5;
• Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups;
• J is oxygen, sulfur, or nitrogen;
• A is an element selected from Group IVa of the Periodic Table of Elements;
• R1, R2, and R3 are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms;
• and
• x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, to form a mono-protected, mono-functionalized living polymer;
• coupling said living polymer with at least one other living polymer with a linking agent;
• and
• removing at least one [A(R1R2R3)]x protecting group.