Photoinitiating system for anionic polymerization

A polymerizable composition, comprising:

• a photoinitiator having a formula
• or salts thereof, wherein:
• R1 and R2 independently are selected from hydrogen, C1-10alkyl, substituted C1-10alkyl, C1-10heteroalkyl, substituted C1-10heteroalkyl, C3-10cycloalkyl, substituted C3-10cycloalkyl, C2-10heterocycloalkyl, substituted C2-10heterocycloalkyl, C6-15aryl, substituted C6-15aryl, C5-14heteroaryl, substituted C5-14heteroaryl, hydroxyl, C1-10alkoxy, C1-10carboxylester, carboxyl, aldehyde, amino, substituted amino, aminocarbonyl, acylamino, sulfhydryl, C1-10thioether, nitro, halogen, cyano, and combinations thereof;
• or
• if q and r are 2, then two R1 groups may join together to form a fused ring and two R2 groups may join together to form a fused ring;
• R3 is selected from aryl, substituted aryl, heteroaryl, and substituted heteroaryl;
• each of R4 and R5 independently is selected from hydrogen, C1-10alkyl, substituted C1-10alkyl, C1-10heteroalkyl, substituted C1-10heteroalkyl, C3-10cycloalkyl, substituted C3-10cycloalkyl, C2-10heterocycloalkyl, substituted C2-10heterocycloalkyl, C6-15aryl, substituted C6-15aryl, C5-14heteroaryl, substituted C5-14heteroaryl, hydroxyl, C1-10alkoxy, C1-10carboxylester, carboxyl, aldehyde, amino, substituted amino, aminocarbonyl, acylamino, sulfhydryl, C1-10thioether, nitro, halogen, cyano, and combinations thereof;
• or
• X is selected from CH2, oxygen, sulfur, or NRa wherein Ra is selected from hydrogen, C1-10alkyl, C1-10cycloalkyl, or C6-15aryl;
• Y is selected from CH2, sulfur, oxygen, NRa wherein Ra is hydrogen, C1-10alkyl, C1-10cycloalkyl, or C6-15aryl;
• each of m, p, and s independently is zero or 1;
• q is 0, 1, 2, 3, or 4;
• and
• r is 0, 1, 2, or 3;
• and
• a polymerizable monomer having a formula selected from
• wherein R6, R7, and R9 independently are selected from hydrogen, C1-10alkyl, substituted C1-10alkyl, C1-10heteroalkyl, substituted C1-10heteroalkyl, C3-10cycloalkyl, substituted C3-10Cycloalkyl, C2-10heterocycloalkyl, substituted C2-10heterocycloalkyl, C6-15aryl, substituted C6-15aryl, C5-14heteroaryl, substituted C5-14heteroaryl, hydroxyl, C1-10alkoxy, C1-10carboxylester, carboxyl, aldehyde, amino, substituted amino, aminocarbonyl, acylamino, sulfhydryl, C1-10thioether, nitro, halogen, cyano, and combinations thereof;
• R15 is selected from hydrogen, alkyl, and aryl;
• R16 is selected from hydrogen, hydroxyl, C1-10alkoxy, amine, substituted amine, and alkoxy-aryl;
• and X is selected from CH2, oxygen, sulfur, or NRa wherein Ra is selected from hydrogen, C1-10alkyl, C1-10cycloalkyl, or C6-15aryl.

A method for making a polymeric compound, comprising:

• providing a photoinitiator having a formula
• wherein:
• R1 and R2 independently are selected from hydrogen, C1-10alkyl, substituted C1-10alkyl, C1-10heteroalkyl, substituted C1-10heteroalkyl, C3-10cycloalkyl, substituted C3-10cycloalkyl, C2-10heterocycloalkyl, substituted C2-10heterocycloalkyl, C6-15aryl, substituted C6-15aryl, C5-14heteroaryl, substituted C5-14heteroaryl, hydroxyl, C1-10alkoxy, C1-10carboxylester, carboxyl, aldehyde, amino, substituted amino, aminocarbonyl, acylamino, sulfhydryl, C1-10thioether, nitro, halogen, cyano, and combinations thereof;
• or
• if q and r are 2, then two R1 groups may join together to form a fused ring and two R2 groups may join together to form a fused ring;
• R3 is selected from aryl, substituted aryl, heteroaryl, and substituted heteroaryl;
• each of R4 and R5 independently is selected from hydrogen, C1-10alkyl, substituted C1-10alkyl, C1-10heteroalkyl, substituted C1-10heteroalkyl, C3-10cycloalkyl, substituted C3-10cycloalkyl, C2-10heterocycloalkyl, substituted C2-10heterocycloalkyl, C6-15aryl, substituted C6-15aryl, C5-14heteroaryl, substituted C5-14heteroaryl, hydroxyl, C1-10alkoxy, C1-10carboxylester, carboxyl, aldehyde, amino, substituted amino, aminocarbonyl, acylamino, sulfhydryl, C1-10thioether, nitro, halogen, cyano, and combinations thereof;
• or
• X is selected from CH2, oxygen, sulfur, or NRa wherein Ra is selected from hydrogen, C1-10alkyl, C1-10cycloalkyl, or C6-15aryl;
• Y is selected from CH2, sulfur, oxygen, NRa wherein Ra is hydrogen, C1-10alkyl, C1-10cycloalkyl, or C6-15aryl;
• each of m, p, and s independently is zero or 1;
• q is 0, 1, 2, 3, or 4;
• r is 0, 1, 2, or 3;
• providing a polymerizable monomer having a formula selected from
• wherein R6, R7, and R9 independently are selected from hydrogen, C1-10alkyl, substituted C1-10alkyl, C1-10heteroalkyl, substituted C1-10heteroalkyl, C3-10cycloalkyl, substituted C3-10Cycloalkyl, C2-10heterocycloalkyl, substituted C2-10heterocycloalkyl, C6-15aryl, substituted C6-15aryl, C5-14heteroaryl, substituted C5-14heteroaryl, hydroxyl, C1-10alkoxy, C1-10carboxylester, carboxyl, aldehyde, amino, substituted amino, aminocarbonyl, acylamino, sulfhydryl, C1-10thioether, nitro, halogen, cyano, and combinations thereof;
• R15 is selected from hydrogen, alkyl, and aryl;
• R16 is selected from hydrogen, hydroxyl, C1-10alkoxy, amine, substituted amine, and alkoxy-aryl;
• and X is selected from CH2, oxygen, sulfur, or NRa wherein Ra is selected from hydrogen, C1-10alkyl, C1-10cycloalkyl, or C6-15aryl;
• exposing the photoinitiator to an energy source;
• and
• combining the photoinitiator and the polymerizable monomer.