Polymeric photoinitiators and photoinitiator monomers

A polymeric photoinitiator, comprising a co-polymer of at least one monomer (A) with at least one monomer (B), wherein:

• monomer (A) is a photoinitiator monomer comprising formula (I):
• wherein:
• Pi is a photoinitiator moiety;
• Y is:
• Z is a linker moiety selected from an optionally substituted —O—(C1-C12 alkylene)-, an optionally substituted —S—(C1-C12 alkylene)-, and an optionally substituted —NR2—(C1-C12 alkylene)-;
• —X1—W1 and —X2—W2 are each independently attached to Y via the Z-linker;
• —X1—W1 and —X2—W2 may be attached to the Z-linker wherever it is chemically feasible, corresponding to formula (IIa):
• R2 is an optionally substituted C1-C12 alkyl;
• X1 and X2 are each independently selected from a single bond, an optionally substituted C1-C12 alkylene, an optionally substituted C2-C12 alkenylene, —O—, —S—, —NR4—, —C(═O)—, —C(═NR3)—, —Si(R3)2—O—, an optionally substituted C3-C8 cycloalkyl, an optionally substituted heterocyclyl, an optionally substituted aryl, and combinations thereof;
• Z is selected such that N is a tertiary amine;
• R3 is H or an optionally substituted C1-C12 alkyl;
• R4 is an optionally substituted C1-C12 alkyl;
• R5 and R6 are each independently selected from an optionally substituted C1-C6 alkyl, wherein the carbon atom adjacent to the N-atom is in a —CH2— moiety;
• W1 and W2 are each independently selected from —OH, —CH2OH, —NH2, —NHR8, —SH, —NCO, —NCS, and —COOH;
• R8 is a C1-C6 alkyl;
• and
• any optional substituents are selected from —F, —Cl, —Br, —I, —CN, —NO2, —C1-C6 alkyl, aryl, —O—(C1-C6 alkyl), —C(O)—O—(C1-C6 alkyl), —S—(C1-C6 alkyl), —S(O)—(C1-C6 alkyl), —SO2—(C1-C6 alkyl), —NH—C(O)—(C1-C6 alkyl), —C(O)—NH—(C1-C6 alkyl), and —C(O)—NH2;
• monomer (B) comprises formula (VI):
• W3-Q-W4 (VI)
• Q is selected from the group consisting of an optionally substituted C1-C12 alkylene, an optionally substituted C2-C12 alkenylene, an optionally substituted C3-C8 cycloalkyl, an optionally substituted C3-C12 heterocyclyl, an optionally substituted aryl, an optionally substituted biaryl, a —[O—(C1-C12 alkylene)]m-, a —[S—(C1-C12 alkylene)]m-, where m is an integer from 1-1000, and combinations thereof;
• W3 and W4 each independently selected from —OH, —CH2OH, —NH2, —NHR11, —SH, —Si(OR11)2—H,
• —C(═O)—OSi(R11)3, —NCO, —NCS, —COOH, —COOR11, —COO-aryl, —C(═O)—Cl, —C(O)—NH2, —C(O)—NHR10, —NH—C(O)—OR10, and —OC(O)—NHR10;
• wherein R10 is H or C1-C6 alkyl, and R11 is C1-C6 alkyl;
• wherein W1, W2, W3 and W4 are selected such W1 reacts with W3 to form a urethane, thiourethane, urea, thiourea, ester, ether, amide, carbonate, allophanate or biuret moiety, and W2 reacts with W4 to form a urethane, thiourethane, urea, thiourea, ester, ether, amide, carbonate, allophanate or biuret moiety.