Polymers comprising in their skeleton an endo ethylenic unsaturation, and preparation processes therefor

Process for preparing a polymer corresponding to formula (II′) below:

• wherein:
• R1 represents a hydrogen atom or a hydrocarbon-based group chosen from linear or branched alkyl groups containing from 1 to 20 carbon atoms, cycloalkyl groups containing from 3 to 8 carbon atoms, alkoxy groups containing from 1 to 20 carbon atoms, aryl groups containing from 6 to 20 carbon atoms and aryloxy groups containing from 6 to 20 carbon atoms;
• R′2 represents a hydrogen or halogen atom or a hydrocarbon-based group chosen from linear or branched alkyl groups containing from 1 to 20 carbon atoms, cycloalkyl groups containing from 3 to 8 carbon atoms, alkoxy groups containing from 1 to 20 carbon atoms, aryl groups containing from 6 to 20 carbon atoms and aryloxy groups containing from 6 to 20 carbon atoms;
• the radicals R3 and R4, which may be identical or different, correspond to the same definition as R1, on condition that at least one of the radicals R3 and R4 represents, in each unit, a hydrogen atom;
• the said radicals R1, R′2, R3 and R4 possibly comprising, when they represent a hydrocarbon-based group, one or more substituents chosen from halogen groups, alkyl groups of 1 to 20 carbon atoms, alkoxy groups of 1 to 20 carbon atoms, aryl groups of 6 to 20 carbon atoms, aryloxy groups of 6 to 20 carbon atoms and amino groups, and R5, R6 and p wherein R5 represents a linear or branched alkyl group containing from 1 to 20 carbon atoms, a cycloalkyl group containing from 3 to 20 carbon atoms or an aryl group containing from 6 to 20 carbon atoms, R6 represents an —OH, primary amine, thiol —SH, halogen or —CHO group, a group derived from —CHO, an ester group, an optionally substituted amide group or an azide group —N3, and p is an integer ranging from 4 to 10 000, the said process comprising a step of reacting, in suitable amount:
• a boron compound of formula (1) R5—BR11R12 with R5 having the same definition as above and representing the group capable of migrating, R11 and R12, which may be identical or different, possibly:
• representing a branched alkyl group linked to the boron via a tertiary carbon containing from 4 to 20 carbon atoms, an alkoxy group containing from 1 to 20 carbon atoms or an aryloxy group containing from 1 to 20 carbon atoms;
• or
• together forming a group —O—X—O—, in which X is a linear or branched alkylenediyl group containing from 2 to 6 carbon atoms
• with at least one allylic nucleophilic ylide compound of formula (2) as defined below,
• E being a leaving group, by means of which an intermediate of formula (XII) below is obtained:
• the said process also comprising a step of converting the boron-based group into a suitable group R6, by means of which the polymer of formula (II′) defined above is obtained.

Process for preparing a polymer corresponding to formula (II′) below:

• wherein:
• R1 represents a hydrogen atom or a hydrocarbon-based group chosen from linear or branched alkyl groups containing from 1 to 20 carbon atoms, cycloalkyl groups containing from 3 to 8 carbon atoms, alkoxy groups containing from 1 to 20 carbon atoms, aryl groups containing from 6 to 20 carbon atoms and aryloxy groups containing from 6 to 20 carbon atoms;
• R′2 represents a hydrogen or halogen atom or a hydrocarbon-based group chosen from linear or branched alkyl groups containing from 1 to 20 carbon atoms, cycloalkyl groups containing from 3 to 8 carbon atoms, alkoxy groups containing from 1 to 20 carbon atoms, aryl groups containing from 6 to 20 carbon atoms and aryloxy groups containing from 6 to 20 carbon atoms;
• the radicals R3 and R4, which may be identical or different, correspond to the same definition as R1, on condition that at least one of the radicals R3 and R4 represents, in each unit, a hydrogen atom;
• the said radicals R1, R′2, R3 and R4 possibly comprising, when they represent a hydrocarbon-based group, one or more substituents chosen from halogen groups, alkyl groups of 1 to 20 carbon atoms, alkoxy groups of 1 to 20 carbon atoms, aryl groups of 6 to 20 carbon atoms, aryloxy groups of 6 to 20 carbon atoms and amino groups, and R5, R6 and p wherein R5 represents a linear or branched alkyl group containing from 1 to 20 carbon atoms, a cycloalkyl group containing from 3 to 20 carbon atoms or an aryl group containing from 6 to 20 carbon atoms, R6 represents an —OH, primary amine, thiol —SH, halogen or —CHO group, a group derived from —CHO, an ester group, an optionally substituted amide group or an azide group —N3, and p is an integer ranging from 4 to 10 000, the said process comprising a step of reacting, in suitable amount, a boron compound of formula (R5)3—B with R5 having the same definition as that given above,
• with at least one allylic nucleophilic ylide compound of formula (2) as defined below,
• E being a leaving group, by means of which an intermediate of formula (XIII) below is obtained:
• the said process also comprising a step of converting the boron-based group into a suitable group R6, by means of which the polymer of formula (II′) defined above is obtained.

Process for preparing the polymer corresponding to the following formula:

• the radicals R5, which may be identical or different, wherein R5 represents a linear or branched alkyl group containing from 1 to 20 carbon atoms, a cycloalkyl group containing from 3 to 20 carbon atoms or an aryl group containing from 6 to 20 carbon atoms, R1, R′2, R3 and R4 being defined as follows:
• R1 represents a hydrogen atom or a hydrocarbon-based group chosen from linear or branched alkyl groups containing from 1 to 20 carbon atoms, cycloalkyl groups containing from 3 to 8 carbon atoms, alkoxy groups containing from 1 to 20 carbon atoms, aryl groups containing from 6 to 20 carbon atoms and aryloxy groups containing from 6 to 20 carbon atoms;
• R′2 represents a hydrogen or halogen atom or a hydrocarbon-based group chosen from linear or branched alkyl groups containing from 1 to 20 carbon atoms, cycloalkyl groups containing from 3 to 8 carbon atoms, alkoxy groups containing from 1 to 20 carbon atoms, aryl groups containing from 6 to 20 carbon atoms and aryloxy groups containing from 6 to 20 carbon atoms;
• the radicals R3 and R4, which may be identical or different, correspond to the same definition as R1, on condition that at least one of the radicals R3 and R4 represents, in each unit, a hydrogen atom;
• the said radicals R1, R′2, R3 and R4 possibly comprising, when they represent a hydrocarbon-based group, one or more substituents chosen from halogen groups, alkyl groups of 1 to 20 carbon atoms, alkoxy groups of 1 to 20 carbon atoms, aryl groups of 6 to 20 carbon atoms, aryloxy groups of 6 to 20 carbon atoms and amino groups, and p1, p2 and p3, which may be identical or different, being integers ranging from 2 to 5000, the said process comprising a step of reacting, in suitable amount, a boron compound of formula (R5)3—B with at least one allylic nucleophilic ylide compound of formula (2) as defined below,
• E being a leaving group, by means of which an intermediate of formula (XIV) below is obtained:
• the said process also comprising a step of converting the boron-based group into a C—OH group by treatment of the intermediate compound (XIV) by heating in the presence of carbon monoxide, followed by a treatment with aqueous hydrogen peroxide solution in basic medium.

Process for preparing a polymer of formula (IV′) below:

• with R1, R′2, R3 and R4 defined as follows,
• R1 represents a hydrogen atom or a hydrocarbon-based group chosen from linear or branched alkyl groups containing from 1 to 20 carbon atoms, cycloalkyl groups containing from 3 to 8 carbon atoms, alkoxy groups containing from 1 to 20 carbon atoms, aryl groups containing from 6 to 20 carbon atoms and aryloxy groups containing from 6 to 20 carbon atoms;
• R′2 represents a hydrogen or halogen atom or a hydrocarbon-based group chosen from linear or branched alkyl groups containing from 1 to 20 carbon atoms, cycloalkyl groups containing from 3 to 8 carbon atoms, alkoxy groups containing from 1 to 20 carbon atoms, aryl groups containing from 6 to 20 carbon atoms and aryloxy groups containing from 6 to 20 carbon atoms;
• the radicals R3 and R4, which may be identical or different, correspond to the same definition as R1, on condition that at least one of the radicals R3 and R4 represents, in each unit, a hydrogen atom;
• the said radicals R1, R′2, R3 and R4 possibly comprising, when they represent a hydrocarbon-based group, one or more substituents chosen from halogen groups, alkyl groups of 1 to 20 carbon atoms, alkoxy groups of 1 to 20 carbon atoms, aryl groups of 6 to 20 carbon atoms, aryloxy groups of 6 to 20 carbon atoms and amino groups, and
• R7, R8, A, m and n wherein A represents a C═O group, a CO derivative or —CHOH group, and the radicals R7 and R8, which may be identical or different, represent a linear or branched alkyl group containing from 1 to 20 carbon atoms, a cycloalkyl group containing from 3 to 20 carbon atoms or an aryl group containing from 6 to 20 carbon atoms, m is an integer ranging from 2 to 5000 and n is an integer ranging from 2 to 5000, the said process comprising the reaction of a boron compound of formula (6) R7—BR8R13 with R7 and R8 having the same definition as that given above, R13 being a branched alkyl group linked to the boron via a tertiary carbon containing from 4 to 20 carbon atoms, or an alkoxy or aryloxy group containing from 1 to 20 carbon atoms, with at least one allylic nucleophilic ylide compound of formula (2):
• E being a leaving group, by means of which a derivative of formula (XV) is obtained:
• followed by a reaction for conversion of the group BR13 into a suitable group A.

Process for preparing a polymer of formula (VII′) below:

• with the radicals R1, R′2, R3 and R4 defined as follows:
• R1 represents a hydrogen atom or a hydrocarbon-based group chosen from linear or branched alkyl groups containing from 1 to 20 carbon atoms, cycloalkyl groups containing from 3 to 8 carbon atoms, alkoxy groups containing from 1 to 20 carbon atoms, aryl groups containing from 6 to 20 carbon atoms and aryloxy groups containing from 6 to 20 carbon atoms;
• R′2 represents a hydrogen or halogen atom or a hydrocarbon-based group chosen from linear or branched alkyl groups containing from 1 to 20 carbon atoms, cycloalkyl groups containing from 3 to 8 carbon atoms, alkoxy groups containing from 1 to 20 carbon atoms, aryl groups containing from 6 to 20 carbon atoms and aryloxy groups containing from 6 to 20 carbon atoms;
• the radicals R3 and R4, which may be identical or different, correspond to the same definition as R1, on condition that at least one of the radicals R3 and R4 represents, in each unit, a hydrogen atom;
• the said radicals R1, R′2, R3 and R4 possibly comprising, when they represent a hydrocarbon-based group, one or more substituents chosen from halogen groups, alkyl groups of 1 to 20 carbon atoms, alkoxy groups of 1 to 20 carbon atoms, aryl groups of 6 to 20 carbon atoms, aryloxy groups of 6 to 20 carbon atoms and amino groups,
• R9, R10, D, m and n wherein the radicals R9 and R10, which may be identical or different, represent an OH, NH2, SH, optionally substituted amide or —CHO group, a group derived from —CHO, an ester group, an optionally substituted amide group or an azide group —N3;
• or R9 and R10 together form a —C(═O)— group, a group derived from CO or a —CHOH— group;
• D represents a linear or branched alkylenediyl group containing from 4 to 20 carbon atoms, possibly comprising in its chain one or more heteroatoms chosen from oxygen, sulfur and nitrogen, m is an integer ranging from 2 to 5000 and n is an integer ranging from 2 to 5000, the said process comprising a step of reacting a cyclic boron compound of formula (7):
• R14 representing a group chosen from branched alkyl groups linked to boron via a tertiary carbon containing from 4 to 20 carbon atoms, or alkoxy or aryloxy groups containing from 1 to 20 carbon atoms,
• with at least one nucleophilic ylide compound of formula (2):
• E being a leaving group, in order to obtain a derivative of formula (XVI):
• followed by a step of conversion of the group BR14 into suitable groups R9 and R10.