Photoacid generator compound, polymer comprising end groups containing the photoacid generator compound, and method of making
View Patent ↗A compound has formula (I): wherein in formula (I), Z is a y valent C 1-20 organic group, A 1 and A 2 are each independently ester containing or non-ester containing and are fluorinated or non-fluorinated, and are independently C 1-40 alkylene, C 3-40 cycloalkylene, C 6-40 arylene, or C 7-40 aralkylene, and A 1 contains a nitrile, ester, or aryl substituent group alpha to the point of attachment with sulfur, L is a heteroatom or a single bond, X 1 is a single bond, —O—, —S—, —C(═O)—O—, —O—C(═O)—, —O—C(═O)—O—, —C(═O)—NR—, —NR—C(═O)—, —NR—C(═O)—NR—, —S(═O) 2 —O—, —O—S(═O) 2 —O—, —NR—S(═O) 2 —, or —S(═O) 2 —NR, wherein R is H, C 1-10 alkyl, C 3-10 cycloalkyl or C 6-10 aryl, Q − is an anionic group, G + is a metallic or non-metallic cation, and y is an integer from 1 to 6. A polymer having end groups comprising the reaction product of the compound of formula (I), and a method of making a polymer, are also disclosed.
1. A compound having formula (I):
wherein in formula (I):
Z is a y valent C 1-20 organic group,
A 1 and A 2 are each independently ester containing or non-ester containing and are fluorinated or non-fluorinated, and are independently C 1-40 alkylene, C 3-40 cycloalkylene, C 6-40 arylene, or C 7-40 aralkylene, and A 1 contains a nitrile, ester, or aryl substituent group alpha to the point of attachment with sulfur,
L is a heteroatom or a single bond,
X 1 is a single bond, —O—, —S—, —C(═O)—O—, —O—C(═O)—, —O—C(═O)—O—, —C(═O)—NR—, —NR—C(═O)—, —NR—C(═O)—NR—, —S(═O) 2 —O—, —O—S(═O) 2 —O—, —NR—S(═O) 2 —, or —S(═O) 2 —NR—, wherein R is H, C 1-10 alkyl, C 3-10 cycloalkyl or C 6-10 aryl,
Q − is an anionic group,
G + is a metallic or non-metallic cation, and
y is an integer from 1 to 6.
2. The compound of claim 1 , wherein
Z is a C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, or C 7-20 aralkyl,
y is an integer from 1 to 4,
A 1 is a C 1-20 alkylene, C 3-20 cycloalkylene, C 6-20 arylene, or C 7-20 aralkylene substituted alpha to the point of attachment with sulfur with a CN, C 6-10 aryl, or a C 2-10 ester-containing organic group,
A 2 is fluorinated or non-fluorinated, and is C 1-20 alkylene, C 3-20 cycloalkylene, C 6-20 arylene, or C 7-20 aralkylene,
Q − is sulfonate, sulfate, sulfonamide anion, or sulfonimide anion group, and
G is an alkali metal cation, ammonium cation, alkylammonium cation, alkyl-aromatic ammonium cation, sulfonium cation, iodonium cation, phosphonium cation, or a carbonium cation.
3. The compound of claim 1 , the compound having formula (I-a):
wherein L, A 1 , A 2 and G are as defined in formula (I), and Z 1 is a substituted or unsubstituted C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, or C 7-20 aralkyl.
4. The compound of claim 3 , the compound having formula (I-b) or (I-c):
wherein L, A 1 , and G are as defined in Formula (I-a), Z 1 is a substituted or unsubstituted C 1-10 alkyl, C 3-10 cycloalkyl, C 6-10 aryl, or C 7-10 aralkyl, and R 1 , R 2 and R 3 are independently H, F, C 1-10 alkyl, C 1-10 fluoroalkyl, C 3-10 cycloalkyl, or C 3-10 fluorocycloalkyl, p is an integer of from 0 to 10, q is an integer of from 1 to 10, and r is an integer of 0 to 4.
5. The compound of claim 4 , having formula (I-b-1):
wherein Z 1 , L, A 1 , and G are as defined in formula (I-b), and R 1 is H, F, C 1-10 alkyl, or C 1-10 fluoroalkyl, p is an integer of from 1 to 10, and q is an integer of from 1 to 10.
6. The compound of claim 3 , the compound having formula (I-d):
wherein Z 1 , L, A 2 and G are as defined in Formula (I-a), each R 4 is independently H, CN, C 6-10 aryl, or —C(═O)—OR 5 where R 5 is a C 1-10 alkyl or C 3-10 cycloalkyl, provided at least one R 4 is not H, and A 3 is ester-containing or non-ester containing and is C 1-10 alkylene, C 3-10 cycloalkylene, C 6-10 arylene, or C 7-10 aralkylene.
7. The compound of claim 1 , wherein G + is a cation of formula (II):
wherein X a is I or S, each R a and R b is independently substituted or unsubstituted and is a lone pair of electrons, C 1-20 alkyl, C 1-20 fluoroalkyl, C 3-20 cycloalkyl, C 3-20 fluorocycloalkyl, C 2-20 alkenyl, C 2-20 fluoroalkenyl, C 6-20 aryl, C 6-20 fluoroaryl, C 7-20 aralkyl, or C 7-20 fluoroaralkyl, wherein where X a is S, R a and R b are separate or connected to each other by a single bond, and where X a is I, one of R a or R b is a lone pair of electrons, and Ar is a C 5-30 aromatic-containing group.
8. The compound of claim 1 chosen from formulas (I-d-1) to (I-d-6):
wherein G + is as defined for formula (I) and R 4 is CN, C 6 aryl, or —C(═O)—OR 5 where R 5 is a C 1-3 alkyl.
9. A polymer comprising end groups derived from the reaction product of the compound of claim 1 , an unsaturated monomer, and optionally, an initiator.
10. A method of making a polymer, comprising:
polymerizing one or more unsaturated monomers in the presence of a compound having formula (I):
wherein in formula (I):
Z is a y valent C 1-20 organic group,
A 1 and A 2 are each independently ester containing or non-ester containing and are fluorinated or non-fluorinated, and are independently C 1-40 alkylene, C 3-40 cycloalkylene, C 6-40 arylene, or C 7-40 aralkylene, and A 1 contains a nitrile, ester, or aryl substituent group alpha to the point of attachment with sulfur,
L is a heteroatom or a single bond,
X 1 is a single bond, —O—, —S—, —C(═O)—O—, —O—C(═O)—, —O—C(═O)—O—, —C(═O)—NR—, —NR—C(═O)—, —NR—C(═O)—NR—, —S(═O) 2 —O—, —O—S(═O) 2 —O—, —NR—S(═O) 2 —, or —S(═O) 2 —NR—, wherein R is H, C 1-10 alkyl, C 3-10 cycloalkyl or C 6-10 aryl,
Q − is an anionic group,
G + is a metallic or non-metallic cation, and
y is an integer from 1 to 6; and
optionally, an initiator.