Polymeric photoinitiators and photoinitiator monomers
The present invention provides polymeric quaternary ammonium photoinitiators being co-polymers of photoinitiator monomers, as well as quaternary ammonium photoinitiator monomer being valuable intermediates in the preparation of such polymeric photoinitiators. Additionally, there is provided a polyacrylate obtained by radical polymerization of at least one acrylate monomer (Ac) in the presence of such polymeric photoinitiators. In the photoinitiator monomers and polymeric photoinitiators, a photoinitiator moiety and a quaternary ammonium are incorporated into the photoinitiator structure.
1. 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 (A) comprising formula (I):
wherein:
Pi is a photoinitiator moiety;
Z is a linker moiety, wherein Z is selected from the group consisting of a single bond, an optionally substituted C 1 -C 12 alkylene, an optionally substituted C 2 -C 12 an alkenylene, —O—, —S—, —NR 2 —, —C(═O)—, —C(═O)—NR 7 —, —NR 7 —C(═O)—, —C(═NR 7 )—, —SO 2 —, —P(═O)(OR 7 )—, an optionally substituted —C 3 -C 8 cycloalkyl, an optionally substituted heterocyclyl, an optionally substituted aryl, —[O—(C 1 -C 12 alkylene)] n -, —[NR 2 —(C 1 -C 12 alkylene)] n , —[S—(C 1 -C 12 alkylene)] n -, and combinations thereof, wherein R 2 is an optionally substituted C 1 -C 12 alkyl, R 7 is H or an optionally substituted C 1 -C 12 alkyl, and n is an integer from 1-20;
R 1 is selected from an optionally substituted C 1 -C 30 alkyl, an optionally substituted C 3 -C 30 alkenyl, an optionally substituted C 3 -C 30 alkynyl, an optionally substituted C 3 -C 12 cycloalkyl, an optionally substituted —[(C 1 -C 6 alkylene)-O—(C 1 -C 6 alkylene)] p -H moiety, an optionally substituted heterocyclyl, and an optionally substituted aryl;
p is an integer from 1-6;
X 1 and X 2 are each independently selected from an optionally substituted C 1 -C 12 alkylene, an optionally substituted C 2 -C 12 alkenylene, —O—, —S—, —NR 4 —, —C(═O)—, —C(═NR 3 )—, —Si(R 3 ) 2 —O—, an optionally substituted C 3 -C 8 cycloalkyl, an optionally substituted heterocyclyl, an optionally substituted aryl, and combinations thereof;
X 1 and X 2 or a part thereof may be linked to one another or to linker Z or R 1 , to form one or more ring structures;
Z, R 1 , X 1 and X 2 are selected such that N is a quaternary ammonium;
R 3 is H or an optionally substituted C 1 -C 12 alkyl;
R 4 is an optionally substituted C 1 -C 12 alkyl;
X − is a counterion, or a negatively charged moiety that is associated with any carbon atom of Pi, Z, R 1 , X 1 , X 2 or their optional substituents, to form a betaine-type structure;
W 1 and W 2 are each independently selected from —OH, —CH 2 OH, —NH 2 , —NHR 6 , —SH, —Si(OR 6 ) 2 —H, —SiH(R 6 ) 2 , —C(═O)—OSi(R 6 ) 3 , —NCO, —NCS, —COOH, —COOR 6 , —COO-aryl, —C(═O)—Cl, —O—C(═O)—Cl, —C(O)—NH 2 , —C(O)—NHR 5 , —NH—C(O)—OR 5 , and —OC(O)—NHR 5 ;
R 5 is H or a C 1 -C 6 alkyl;
R 6 is a C 1 -C 6 alkyl;
monomer (B) comprises formula (VI):
W 3 -Q-W 4 (VI)
wherein W 3 and W 4 are each independently selected from halogen, —OH, —CH 2 OH, —NH 2 , —HNR 10 , —SH, Si(OR 10 ) 2 —H, —SiH(R 10 ) 2 , —C(═O)—OSi(R 10 ) 3 , —NCO, —NCS, —COOH, COOR 10 , —C) aryl, —C(═O)—Cl, —O—C═O Cl, —C(O)—NH 2 , —C(O)—NHR 9 , —NH—C(O)—OR 9 and —OC(O)—NHR 9 , wherein R 9 is H or a C 1 -C 6 alkyl and R 10 is a C 1 -C 6 alkyl;
Q is selected from the group consisting of an optionally substituted C 1 -C 12 alkylene, an optionally substituted C 2 -C 12 alkenylene, an optionally substituted C 3 -C 8 cycloalkyl, an optionally substituted C 3 -C 12 heterocyclyl, an optionally substituted aryl, an optionally substituted biaryl, and combinations thereof, or optionally Q can be a Pi; and
wherein W 1 , W 2 , W 3 and W 4 are selected such that (A) and (B) react such that W 1 reacts with W 3 to from a urethane, a thiourethane, a urea, a thiourea, an ester, an ether, an amide, a carbonate, an allophanate, or a biuret moiety and W 2 reacts with W 4 to form a urethane, a thiourethane, a urea, a thiourea, an ester, an ether, an amide, a carbonate, an allophanate, or a biuret moiety.
2. The polymeric photoinitiator according to claim 1 , wherein n is an integer from 1-10.
3. The polymeric photoinitiator according to claim 1 , wherein Z is selected from a single bond, an optionally substituted C 1 -C 12 alkylene, an optionally substituted C 2 -C 12 alkenylene, —O—, —S—, —NR 2 —, —C(═O)—, —C(═O)—NR 7 —, —NR 7 —C(═O)—, —C(═NR 7 )—, an optionally substituted —C 3 -C 8 cycloalkyl, an optionally substituted heterocyclyl, an optionally substituted aryl, —[O—(C 1 -C 12 alkylene)] n —, —[NR 2 —(C 1 -C 12 alkylene)] n , —[S—(C 1 -C 12 alkylene)] n -, and combinations thereof, wherein R 2 is an optionally substituted C 1 -C 12 alkyl, R 7 is H or an optionally substituted C 1 -C 12 alkyl, and n is an integer from 1-20.
4. The polymeric photoinitiator, according to claim 1 , wherein formula (I) comprises formula (II) wherein Z is -Za-Zb-:
wherein:
Pi is a photoinitiator moiety;
Za and Zb together form a single bond, or a linker in which Za is selected from an optionally substituted —[O—(C 1 -C 12 alkylene)] n -, an optionally substituted —[NR 2 —(C 1 -C 12 alkylene)] n , and an optionally substituted —[S—(C 1 -C 12 alkylene)] n -, wherein Za is joined to Pi via the O, N or S atom in Za, and Zb is a linker moiety;
Zb is selected from a single bond, an optionally substituted C 1 -C 12 alkylene, an optionally substituted C 2 -C 12 alkenylene, —O—, —S—, —NR 2 —, —C(═O)—, —C(═O)—NR 7 —, —NR 7 —C(═O)—, —C(═NR 7 )—, —SO 2 —, —P(═O)(OR 7 )—, an optionally substituted C 3 -C 8 cycloalkyl, an optionally substituted heterocyclyl, an optionally substituted aryl, an optionally substituted —[O—(C 1 -C 12 alkylene)] n -, an optionally substituted —[NR 2 —(C 1 -C 12 alkylene)] n , an optionally substituted;
—[S—(C 1 -C 12 alkylene)] n -, and combinations thereof, wherein R 2 is an optionally substituted C 1 -C 12 alkyl, R 7 is H or an optionally substituted C 1 -C 12 alkyl, and n is an integer from 1-20
R 1 is selected from an optionally substituted C 1 -C 30 alkyl, an optionally substituted C 3 -C 30 alkenyl, an optionally substituted C 3 -C 30 alkynyl, an optionally substituted C 3 -C 12 cycloalkyl, an optionally substituted —[(C 1 -C 6 alkylene)-O—(C 1 -C 6 alkylene)] p -H moiety, an optionally substituted heterocyclyl, and an optionally substituted aryl;
R 2 is an optionally substituted C 1 -C 12 alkyl;
n is an integer from 1-20;
p is an integer from 1-6;
X 1 and X 2 are each independently selected from an optionally substituted C 1 -C 12 alkylene, an optionally substituted C 2 -C 12 alkenylene, —O—, —S—, —NR 4 —, —C(═O)—, —C(═NR 3 )—, —Si(R 3 ) 2 —O—, an optionally substituted C 3 -C 8 cycloalkyl, an optionally substituted heterocyclyl, an optionally substituted aryl, and combinations thereof;
X 1 and X 2 or a part thereof may be linked to one another or to linkers Za or Zb, or R 1 to form one or more ring structures;
Za, Zb, R 1 , X 1 and X 2 are selected such that N is a quaternary ammonium;
R 3 is H or an optionally substituted C 1 -C 12 alkyl;
R 4 is an optionally substituted C 1 -C 12 alkyl;
X − is a counterion, or a negatively charged moiety that is associated with any carbon atom of Pi, Za, Zb, R 1 , X 1 , X 2 or their optional substituents to form a betaine-type structure;
W 1 and W 2 are each independently selected from —OH, —CH 2 OH, —NH 2 , —NHR 6 , —SH, —Si(OR 6 ) 2 —H, —SiH(R 6 ) 2 , —C(═O)—OSi(R 6 ) 3 , —NCO, —NCS, —COOH, —COOR 6 , —COO-aryl, —C(═O)—Cl, —O—C(═O)—Cl, —C(O)—NH 2 , —C(O)—NHR 5 , —NH—C(O)—OR 5 , and —OC(O)—NHR 5 ;
R 5 is H or a C 1 -C 6 alkyl; and
R 6 is a C 1 -C 6 alkyl.
5. The polymeric photoinitiator according to claim 4 , wherein n is an integer from 1-10.
6. The polymeric photoinitiator according to claim 4 , wherein Za is selected from —[O—(C 1 -C 6 alkylene)] n -, —[NR 2 —(C 1 -C 6 alkylene)] n , —[S—(C 1 -C 6 alkylene)] n -, —O—(C 1 -C 6 alkylene)-NR 2 —(C 1 -C 6 alkylene)-, —NR 2 —(C 1 -C 6 alkylene)-O—(C 1 -C 6 alkylene)-, —S—(C 1 -C 6 alkylene)-O—(C 1 -C 6 alkylene)-, —O—(C 1 -C 6 alkylene)-S—(C 1 -C 6 alkylene)-, —S—(C 1 -C 6 alkylene)-NR 2 —(C 1 -C 6 alkylene)-, and —NR 2 —(C 1 -C 6 alkylene)-S—(C 1 -C 6 alkylene)-, wherein the C 1 -C 6 alkylene optionally is substituted with one or more substituents, wherein the R 2 is C 1 -C 6 alkyl, and n is an integer from 1-2.
7. The polymeric photoinitiator according to claim 1 , wherein W 1 and W 2 are independently selected from —OH, —CH 2 OH, —NH 2 , —NHR 5 , —SH, —NCO, —NCS, and —COOH.
8. The polymeric photoinitiator according to claim 1 , wherein W 1 and W 2 are the same.
9. The polymeric photoinitiator according to claim 1 , wherein R 1 is selected from an optionally substituted C 1 -C 20 alkyl, an optionally substituted C 3 -C 20 alkenyl, an optionally substituted C 3 -C 20 alkynyl, and an optionally substituted —[(C 1 -C 6 alkylene)-O—(C 1 -C 6 alkylene)] p -H moiety; wherein p is an integer from 1-2.
10. The polymeric photoinitiator according to claim 1 , wherein X − is a counterion selected from fluoride, chloride, bromide, iodide, sulfate, carbonate, phosphate, tetrafluoroborate, tetraarylborate, hexafluorophosphate, alkyl carboxylate, aryl carboxylate, alkyl sulfonate and aryl sulfonate.
11. The polymeric photoinitiator according to claim 1 , wherein X − is a negatively charged moiety that is associated with any carbon atom of Pi, Z, Za, Zb, R 1 , X 1 , X 2 or their optionally substituents to form a betaine-type structure.
12. The polymeric photoinitiator according to claim 1 , wherein X 1 and X 2 are each independently an optionally substituted C 1 -C 12 alkylene.
13. The polymeric photoinitiator according to claim 1 , wherein X 1 and/or X 2 is attached to the N atom of the quaternary ammonium branching group through a —CH 2 — group.
14. The polymeric photoinitiator according to claim 1 , wherein X 1 and X 2 are the same.
15. The polymeric photoinitiator according to claim 1 , wherein X 1 and X 2 are independently selected from an optionally substituted C 1 -C 12 alkylene, and W 1 and W 2 are —CH 2 OH.
16. The polymeric photoinitiator according to claim 1 , wherein one or more optional substitutents are selected from the group consisting of —F, —Cl, —Br, —I, —CN, —NO 2 , —C 1 -C 6 alkyl, —C 2 -C 6 alkenyl, —C 3 -C 6 cycloalkyl, aryl, heterocyclyl, —O—(C 1 -C 6 alkyl), —O—C 3 -C 8 cycloalkyl, —O-aryl, —C(O)—(R 8 ), —C(O)-aryl, —C(O)O—(C 1 -C 6 alkyl), —C(O)O-aryl, —O—C(O)-aryl, —O—C(O)—O—(C 1 -C 6 alkyl), —O—C(O)—O-aryl, —N(C 1 -C 6 alkyl) 2 , —N(C 1 -C 6 alkyl)(C 3 -C 6 cycloalkyl), —N(C 1 -C 6 alkyl)(aryl), —N(aryl) 2 , —N(R 8 )—C(O)—(C 1 -C 6 alkyl), —N(R 8 )—C(O)-aryl, —C(O)—N(R) 2 , —C(O)—N(R 8 )-aryl, —C(O)—N(aryl) 2 , —O—C(O)—N(R) 2 , —O—C(O)—NH—(C 1 -C 6 aryl), —N(R 8 )—C(O)—O—(C 1 -C 6 alkyl), —NH—C(O)—O—(C 1 -C 6 aryl), —S(O)—(C 1 -C 6 alkyl), —S(O)-aryl, —SO 2 —(C 1 -C 6 alkyl), —SO 2 -aryl, —S—(C 1 -C 6 alkyl) and —S-aryl; wherein R 8 is H or C 1 -C 6 alkyl.
17. The polymeric photoinitiator according to claim 1 , wherein Pi is a photoinitiator moiety selected from the group consisting of benzoin ethers, phenyl hydroxyalkyl ketones, phenyl aminoalkyl ketones, benzophenones, thioxanthones, xanthones, acridones, anthraquinones, fluorenones, dibenzosuberones, benzils, benzil ketals, α-dialkoxy-acetophenones, α-hydroxy-alkyl-phenones, α-amino-alkyl-phenones, acyl-phosphine oxides, phenyl ketocoumarins, camphorquinones, silane and derivatives thereof, and maleimides.
18. The polymeric photoinitiator according to claim 1 , wherein Pi is a photoinitiator moiety selected from benzophenones, thioxanthones, benzilketals and phenyl hydroxyalkyl ketones.
19. The polymeric photoinitiator according to claim 1 , wherein Pi is a non-cleavable photoinitiator.
20. The polymeric photoinitiator according to claim 1 , wherein formula (I) comprises formula (IIIa):
wherein Ar 1 and Ar 2 are each independently selected from the same or different aryl, where Z may be present at any position on Ar 2 , and where each aryl independently may be optionally substituted with one or more substituents selected from the substitutents defined in claim 16 .
21. The polymeric photoinitiator according to claim 20 , wherein Ar 1 and Ar 2 each independently are an optionally substituted phenyl.
22. The polymeric photoinitiator according to claim 20 , wherein Z is present at the para-position on Ar 2 .
23. The polymeric photoinitiator according to claim 1 , wherein formula (I) comprises formula (IV):
wherein Z, R 1 , X − , X 1 , X 2 , W 1 and W 2 are as defined in claim 1 , and wherein the aromatic rings of formula (IV) may each independently be optionally substituted.
24. The polymeric photoinitiator according to claim 1 , wherein formula (I) comprises formula (V):
wherein Z, R 1 , X − , X 1 , X 2 , W 1 and W 2 , are as defined in claim 1 , and wherein the aromatic rings of formula (V) may each independently be optionally substituted.
25. The polymeric photoinitiator according to claim 1 , wherein formula (I) comprises formula (IVa):
wherein Z, R 1 , X − , X 1 , X 2 , W 1 and W 2 are as defined in claim 1 , and wherein the aromatic rings each independently may be optionally substituted.
26. The polymeric photoinitiator according to claim 1 , wherein the photoinitiator monomer (A) is selected from the group consisting of:
4-({[(4-benzoylphenyl)methyl]bis(2-hydroxyethyl)ammoniumyl}methyl)benzoate;
[(4-benzoylphenyl)methyl]bis[2-(2-hydroxyethoxy)ethyl]methylammonium bromide;
[2-(4-benzoylphenyl)-2-oxoethyl]bis(2-hydroxyethyl)methylammonium bromide;
[2-(2-benzoylbenzoyloxy)ethyl]bis(2-hydroxyethyl)methylammonium bromide;
[3-(4-benzoylphenoxy)propyl]bis(2-hydroxyethyl)methylammonium bromide;
[3-(4-benzoylphenoxy)propyl](benzyl)bis(2-hydroxyethyl)ammonium bromide;
3-{[3-(4-benzoylphenoxy)propyl]bis(2-hydroxyethyl)ammonium}propane-1-sulfonate;
{2-[(4-benzoylphenyl)sulfanyl]ethyl}(ethyl)bis(2-hydroxyethyl)ammonium iodide;
[2-(4-benzoylphenoxy)ethyl]bis(2-hydroxypropyl)methylammonium 4-methylbenzene-1-sulfonate;
2-{[2-(4-benzoylphenoxy)ethyl]bis(2-hydroxyethyl)ammoniumyl}ethane-1-sulfonate;
2-[bis(2-aminoethyl)[3-(4-benzoylphenoxy)propyl]ammoniumyl]acetate;
{3-[(1-chloro-9-oxo-9H-thioxanthen-4-yl)oxy]propyl}bis(2-hydroxyethyl)methylammonium bromide;
{3-[(1-chloro-9-oxo-9H-thioxanthen-4-yl)oxy]propyl}bis(2-hydroxyethyl)ethylammonium iodide;
2-({3-[(1-chloro-9-oxo-9H-thioxanthen-4-yl)oxy]propyl}bis(2-hydroxyethyl)ammoniumyl)ethane-1-sulfonate;
bis(2-hydroxyethyl)methyl[2-({2-[(9-oxo-9H-thioxanthen-2-yl)oxy]acetyl}oxy)ethyl]ammonium chloride;
(cyanomethyl)({2-[4-(2-hydroxy-2-methylpropanoyl)phenoxy]ethyl})bis(2-hydroxyethyl)ammonium 4-bromobenzene-1-sulfonate; and
benzyl({3-[(1-chloro-9-oxo-9H-thioxanthen-4-yl)oxy]propyl})bis(2-hydroxyethyl)ammonium bromide.
27. The polymeric photoinitiator according to claim 1 , wherein W 3 and W 4 are each independently selected from isocyanate and thioisocyanate groups.
28. The polymeric photoinitiator according to claim 1 , wherein monomer (B) is selected from the group consisting of: 1,4-phenylene diisocyanate (PPDI), toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), 3,3′-bitolylene-4,4′-diisocyanate (TODI), 1,3-xylylenediisocyanate (XDI), tetramethyl-m-xylidene diisocyanate (TMXDI), 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), bis(4-isocyanatocyclohexyl)methane (HMDI), 2,2,5-trimethylhexane diisocyanate (TMHDI), 1,4-cyclohexane diisocyanate (CHDI), and 1,3-bis(isocyanato-methyl)cyclohexane (HXDI).
29. The polymeric photoinitiator according to claim 1 , wherein both W 1 and W 2 are alcohol functional groups and both W 3 and W 4 are isocyanate functional groups.
30. The polymeric photoinitiator according to claim 1 , further comprising one or more additional monomers (C),
wherein monomer (C) has the structure of formula (VII):
W 5 -T-W 6 (VII)
herein T is selected from the group consisting of an optionally substituted C 1 -C 12 alkylene, an optionally substituted C 1 -C 12 alkenylene, an optionally substituted C 3 -C 8 cycloalkyl, an optionally substituted C 3 -C 12 heterocyclyl, an optionally substituted aryl, an optionally substituted biaryl, and combinations thereof;
wherein each of said one or more additional monomers (C) comprises at least two functional groups W 5 and W 6 , said W 5 and W 6 being independently selected from —OH, —CH 2 OH, —NH 2 , —NHR 12 , —SH, —Si(OR 12 ) 2 —H, —C(═O)—OSi(R 12 ) 3 , —SiH(R 12 ) 2 , —NCO, —NCS, —COOH, —COOR 12 , —COO-aryl, —C(═O)—Cl, —O—C(═O)—Cl, —C(O)—NH 2 , —C(O)—NHR 11 , —NH—C(O)—OR 11 , and —OC(O)—NHR 11 , wherein R 11 is H or C 1 -C 6 alkyl, and wherein R 12 is C 1 -C 6 alkyl;
wherein W 5 and W 6 are selected such W 5 reacts with W 1 or W 3 to form a urethane, thiourethane, urea, thiourea, ester, ether, amide, carbonate, allophanate or biuret moiety, and W 6 reacts with W 2 or W 4 to form a urethane, thiourethane, urea, thiourea, ester, ether, amide, carbonate, allophanate or biuret moiety.
31. The polymeric photoinitiator according to claim 30 , wherein W 5 and W 6 are independently selected from —OH, —CH 2 OH, —NH 2 , —NHR 12 , and —SH.
32. The polymeric photoinitiator according to claim 1 , wherein the weight ratio of monomers (A):(B) is 1:99-99:1.