Polymerization process with living characteristics and polymers made therefrom

A process for producing a polymer, said process comprising:

• charging a polymerization medium in a reactor with a chain transfer agent;
• introducing a source of free radicals and a monomer mix into said medium to polymerize said monomer mix into said polymer, said chain transfer agent having a transfer constant in the range of from 0.1 to 5000 and having the following formula:
• wherein when D is D1 of the following formula:
• then p is in the range of from 1 to 200, E is Z′ and said transfer agent is of the following formula:
• wherein when D is D2 of the following formula:
• then p is in the range of from 1 to 200, E is E1 or E2 and said transfer agent is of the following formula:
• wherein when D is D3 of the following formula:
• then p′ is in the range of from 2 to 200, E is Z, E1 or E2 and said transfer agent is of the following formula:
• wherein when D is D4 of the following formula:
• —S—R′
• then E is E3 or E4 and said transfer agent is of the following formula:
• where in all of the above:
• R is a p-valent moiety derived from a moiety selected from the group consisting of substituted or unsubstituted alkane, substituted or unsubstituted alkene, substituted or unsubstituted arene, unsaturated or aromatic carbocyclic ring, unsaturated or saturated heterocyclic ring, an organometallic species, and a polymer chain, R. being a free radical leaving group resulting from R that initiates free radical polymerization;
• R* and R′ are monovalent moieties independently selected from the group consisting of a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, unsaturated or aromatic carbocyclic ring, unsaturated or saturated heterocyclic ring, substituted or unsubstituted alkylthio, substituted or unsubstituted alkoxy, substituted or unsubstituted dialkylamino, an organometallic species, and a polymer chain, R*. being a free radical leaving group resulting from R* that initiates free radical polymerization;
• X is selected from the group consisting of a substituted or unsubstituted methine, nitrogen, and a conjugating group;
• Z′ is selected from the group consisting of E1, E2, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylthio, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted —COOR″, carboxy, substituted or unsubstituted —CONR″2, cyano, —P(═O)(OR″)2, —P(═O)R″2;
• R″ is selected from the group consisting of substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkaryl, and a combination thereof;
• Z″ is a p′-valent moiety derived from a moiety selected from the group consisting of a substituted or unsubstituted alkane, substituted or unsubstituted alkene, substituted or unsubstituted arene, substituted or unsubstituted heterocycle, a polymer chain, an organometallic species, and a combination thereof;
• Z is selected from the group consisting of a halogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylthio, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted —COOR″, carboxy, substituted or unsubstituted —CONR″2, cyano, —P(═O)(OR″)2, —P(═O)R″2;
• E1 is a substituent functionality derived from a substituted or unsubstituted heterocycle attached via a nitrogen atom, or is of the following formula:
• wherein G and J are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted acyl, substituted or unsubstituted aroyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted alkylphosphonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted arylphosphonyl;
• E2 is of the following formula:
• wherein G′ is selected from the group consisting of substituted or unsubstituted alkenyl, substituted or unsubstituted aryl;
• E3 is of the following formula
• wherein p′″ is between 2 and 200, G″ is Z″ and J′ is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted acyl, substituted or unsubstituted aroyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted alkylphosphonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted arylsulfinyl, substituted or
• E4 is of the following formula
• wherein p′″ is between 2 and 200 and G′″ is Z″.
• said monomer mix comprising one or more monomers selected from the group consisting of maleic anhydride, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate, cyclopolymerizable monomer, and vinyl monomer having the formula:
• where L is selected from the group consisting of hydrogen, halogen, and substituted or unsubstituted C1-C4 alkyl, said alkyl substituents being independently selected from the group consisting of hydroxy, alkoxy, OR″, CO2H, O2CR″, CO2R″ and a combination thereof;
• where M is selected from the group consisting of hydrogen, R″, CO2H, CO2R″, COR″, CN, CONH2, CONHR″, CONR″2, O2CR″, OR″, and halogen.

A chain transfer agent having a transfer constant in the range of from 0.1 to 5000, said chain transfer agent having the following formula:

• wherein when D is D1 of the following formula:
• then p is in the range of from 1 to 200, E is Z′ and said transfer agent is of the following formula:
• wherein when D is D2 of the following formula:
• then p is in the range of from 1 to 200, E is E1 or E2 and said transfer agent is of the following formula:
• wherein when D is D3 of the following formula:
• then p′ is in the range of from 2 to 200, E is Z, E1 or E2 and said transfer agent is of the following formula:
• wherein when D is D4 of the following formula:
• —S—R′
• then E is E3 or E4 and said transfer agent is of the following formula:
• where in all of the above:
• R is a p-valent moiety derived from a moiety selected from the group consisting of substituted or unsubstituted alkane, substituted or unsubstituted alkene, substituted or unsubstituted arene, unsaturated or aromatic carbocyclic ring, unsaturated or saturated heterocyclic ring, an organometallic species, and a polymer chain, R. being a free radical leaving group resulting from R that initiates free radical polymerization;
• R* and R′ are monovalent moieties independently selected from the group consisting of a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, unsaturated or aromatic carbocyclic ring, unsaturated or saturated heterocyclic ring, substituted or unsubstituted alkylthio, substituted or unsubstituted alkoxy, substituted or unsubstituted dialkyl amino, an organometallic species, and a polymer chain, R*• being a free radical leaving group resulting from R* that initiates free radical polymerization;
• X is selected from the group consisting of a substituted or unsubstituted methine, nitrogen, and a conjugating group;
• Z′ is selected from the group consisting of E1, E2, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylthio, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted —COOR″, carboxy, substituted or unsubstituted —CONR″2, cyano, —P(═O)(OR″)2, —P(═O)R″2;
• R″ is selected from the group consisting of substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkaryl, and a combination thereof;
• Z″ is a p′-valent moiety derived from a moiety selected from the group consisting of a substituted or unsubstituted alkane, substituted or unsubstituted alkene, substituted or unsubstituted arene, substituted or unsubstituted heterocycle, a polymer chain, an organometallic species, and a combination thereof;
• Z is selected from the group consisting of a halogen, substituted or unsubsfituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylthio, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted —COOR″, carboxy, substituted or unsubstituted —CONR″2, cyano, —P(═O)(OR″)2, —P(═O)R″2;
• E1 is a substituent functionality derived from a substituted or unsubstituted heterocycle attached via a nitrogen atom, or is of the following formula:
• wherein G and J are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted acyl, substituted or unsubstituted aroyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted alkylphosphonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted arylphosphonyl;
• E2 is of the following formula:
• wherein G′ is selected from the group consisting of substituted or unsubstituted alkenyl, substituted or unsubstituted aryl;
• E3 is of the following formula
• wherein p′″ is between 2 and 200, G″ is Z″ and J′ is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted acyl, substituted or unsubstituted aroyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted alkylphosphonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted arylphosphonyl or is joined to G″ so as to form a 5-8 membered ring;
• and
• E4 is of the following formula
• wherein p′″ is between 2 and 200 and G′″ is Z″, with the provisos that when D is D2, p=1 and R′ is benzyl or ring substituted benzyl and E is E1 then G and J are not both alkyl, when D is D2, p=1 and R′ is benzyl and E is E2 then G′ is not alkyl, when D is D2, p=2 and R is p-xylylene and E is E1 then G and J are not hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and when D is D2, p=2 to 12 and R is (—CH2)pY where Y is p-valent moiety and E is E1 then G and J are not substituted or unsubstituted alkyl, substituted or unsubstituted aryl.