Photochemical crosslinkers for polymer coatings and substrate tie-layer

A compound of formula:

• L-(T-C(R1)(XP)CHR2GR3C(═O)R4)m
• wherein
• L is a linking group comprising
• a formula according to structure (I):
• A, B and J form a ring, wherein A and J are C═O;
• B is NR11;
• R11 is a hydrogen atom, an alkyl group, an aryl group or denotes a bond with T;
• T is (—CH2—)x, (—CH2CH2—O—)x, (—CH2CH2CH2—O—)x, (—CH2CH2CH2CH2—O—)x or forms a bond;
• R1 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group;
• X is O, S, or NR8R9;
• P is a hydrogen atom or a protecting group, with the proviso that P is absent when X is NR8R9;
• R2 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group;
• G is, —C(═O)O—, —O—, —NHC(═O)O—, —NHC(═O)S—, —SO2—, —CONH—, —NHCONH—, —NHC(═S)NH—, —NR10—, —SO2NH—, —C(═N)—, —C(═O)— or —(CH2)t—O—;
• R3 and R4 are each independently an alkyl, aryl, arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally, R3 and R4 can be tethered together via (—CH2—)q, (—CH2—)rC═O(—CH2—)s, (—CH2—)rS(—CH2—)s, (—CH2—)rS═O(—CH2—)s or (—CH2—)rS(O)2(—CH2—)s, (—CH2—)rNR(—CH2—)s;
• R1° is a hydrogen atom or an alkyl, aryl or arylalkyl group;
• R8 and R9 are each independently a hydrogen atom, an alkyl, aryl, or arylalkyl group;
• R is a hydrogen atom, an alkyl or aryl group;
• q is an integer from 1 to about 7;
• r is an integer from 0 to about 3;
• s is an integer from 0 to about 3;
• m is an integer from 2 to about 10;
• t is an integer from 1 to about 10;
• and
• x is an integer from 1 to about 500.

A compound of formula:

• L-(GTZR3C(═O)R4)m
• wherein
• L is a linking group comprising
• a formula according to structure (I):
• A, B and J form a ring, wherein A and J are C═O;
• B is NR11;
• R11 is a hydrogen atom, an alkyl group, an aryl group or denotes a bond;
• T is (—CH2—)x, (—CH2CH2—O—)x, (—CH2CH2CH2—O—)x, (—CH2CH2CH2CH2—O—)x or forms a bond;
• G is —C(═O) O—, —NHC(═O) O—, —NHC(═O)S—, —CONH—, —NHCONH—, —NHC(═S)NH—, —C(═N)—, —C(═O)— or —(CH2)t—O—;
• Z is C═O, COO, or CONH when T is (—CH2—)x;
• R3 and R4 are each independently an alkyl, aryl, arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally, R3 and R4 can be tethered together via (—CH2—)q, (—CH2—)rC═O(—CH2—)s, (—CH2—)rS(—CH2—)s, (—CH2—)rS═O(—CH2—)s or (—CH2—)rS(O)2(—CH2—)s, (—CH2—)rNR(—CH2—)s;
• R is a hydrogen atom or an alkyl or aryl group;
• q is an integer from 1 to about 7;
• r is an integer from 0 to about 3;
• s is an integer from 0 to about 3;
• m is an integer from 2 to about 10;
• t is an integer from 1 to about 10;
• and
• x is an integer from 1 to about 500.

A compound of formula:

• L-(TGQR3C(═O)R4)m
• wherein
• L is a linking group comprising
• a formula according to structure (I):
• A, B and J form a ring, wherein A and J are C═O;
• B is NR11;
• R11 is a hydrogen atom, an alkyl group, an aryl group or denotes a bond with T;
• T is (—CH2—)x, (—CH2CH2—O—)x, (—CH2CH2CH2—O—)x, (—CH2CH2CH2CH2—O—)x or forms a bond;
• G is —C(═O)O—, —O—, —NHC(═O)O—, —NHC(═O)S—, —SO2—, —CONH—, —NHCONH—, —NHC(═S)NH—, —NR10—, —SO2NH—, —C(═N)—, —C(═O)— or —(CH2)t—O—;
• Q is (—CH2—)p, (—CH2CH2—O—)p, (—CH2CH2CH2—O—)p or (—CH2CH2CH2CH2—O—)p;
• R3 and R4 are each independently an alkyl, aryl, arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally, R3 and R4 can be tethered together via (—CH2—)q, (—CH2—)rC═O(—CH2—)s, (—CH2—)rS(—CH2—)s, (—CH2—)rS═O(—CH2—)s or (—CH2—)rS(O)2(—CH2—)s, (—CH2—)rNR(—CH2—)s;
• R10 is a hydrogen atom or an alkyl, aryl, or an arylalkyl group;
• R is a hydrogen atom or an alkyl or aryl group;
• q is an integer from 1 to about 7;
• r is an integer from 0 to about 3;
• s is an integer from 0 to about 3;
• m is an integer from 2 to about 10;
• p is an integer from 1 to about 10;
• t is an integer from 1 to about 10;
• and
• x is an integer from 1 to about 500.

A compound of formula:

• L-(—CH2—)xxC(R1)(GR3C(═O)R4)m
• wherein
• L is a linking group comprising
• a formula according to structure (I):
• A, B and J form a ring, wherein A and J are C═O;
• B is NR11;
• R11 is a hydrogen atom, an alkyl group, an aryl group or denotes a bond;
• R1 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl , or aryloxyaryl group;
• each G is —C(═O) O—, —O—, —NHC(═O )O—, —NHC(═O)S—, —SO2—, —CONH—, —NHCONH—, —NHC(═S)NH—, —NR10—, —SO2NH—, —C(═N)—, —C(═O)— or —(CH2)t—O—;
• each R3 and R4 are each independently an alkyl, aryl, arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally, R3 and R4 can be tethered together via (—CH2—)q, (—CH2—)rC═O(—CH2—)s, (—CH2—)rS(—CH2—)s, (—CH2—)rS═O(—CH2—)s or (—CH2—)rS(O)2(—CH2—)s, (—CH2—)rNR(—CH2—)s;
• each R10 is a hydrogen atom or an alkyl, aryl, or an arylalkyl group;
• each R is a hydrogen atom or an alkyl or aryl group;
• each q is an integer from 1 to about 7;
• each r is an integer from 0 to about 3;
• each s is an integer from 0 to about 3;
• m is an integer from 2 to about 10;
• each t is an integer from 1 to about 10;
• and
• xx is an integer from 1 to about 10.

A compound of formula:

• L-(—C(R1)(XP)CHR2GR3C(═O)R4)m
• wherein
• L is a linking group comprising
• a formula according to structure (I):
• A, B and J form a ring, wherein A and J are C═O;
• B is NR11;
• R11 is a hydrogen atom, an alkyl group, an aryl group or denotes a bond;
• R1 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group;
• X is O, S, or NR8R9;
• P is a hydrogen atom or a protecting group, with the proviso that P is absent when X is NR8R9;
• R2 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group;
• G is —C(═O)O—, —O—, —NHC(═O)O—, —NHC(═O)S—, —SO2—, —CONH—, —NHCONH—, —NHC(═S)NH—, —NR10—, —SO2NH—, —C(═N)—, —C(═O)— or —(CH2)t—O—;
• R3 and R4 are each independently an alkyl, aryl, arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally, R3 and R4 can be tethered together via (—CH2—)q, (—CH2—)rC═O(—CH2—)s, (—CH2—)rS(—CH2—)s, (—CH2—)rS═O(—CH2—)s or (—CH2—)rS(O)2(—CH2—)s, (—CH2—)rNR(—CH2—)s;
• R8 and R9 are each independently a hydrogen atom, an alkyl, aryl, or arylalkyl group;
• R10 is a hydrogen atom or an alkyl, aryl, or an arylalkyl group;
• R is a hydrogen atom, an alkyl or an aryl group;
• q is an integer from 1 to about 7;
• r is an integer from 0 to about 3;
• s is an integer from 0 to about 3;
• m is an integer from 2 to about 10;
• and
• t is an integer from 1 to about 10.

A compound of formula:

• L-(GR3C(═O)R4)m;
• wherein
• L is a linking group comprising
• a formula according to structure (I):
• A, B and J form a ring, wherein A and J are C═O;
• B is NR11;
• R11 is a hydrogen atom, an alkyl group, an aryl group or denotes a bond;
• G is —C(═O) O—, —NHC(═O)O—, —NHC(═O)S—, —CONH—, —NHCONH—, —NHC(═S)NH—, —C(═N)—, —C(═O)— or —(CH2)t—O—;
• R3 and R4 are each independently an alkyl, aryl, arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally, R3 and R4 can be tethered together via (—CH2—)q, (—CH2—)rC═O(—CH2—)s, (—CH2—)rS(—CH2—)s, (—CH2—)rS═O(—CH2—)s or (—CH2—)rS(O)2(—CH2—)s, (—CH2—)rNR(—CH2—)s;
• R is a hydrogen atom, an alkyl or an aryl group;
• q is an integer from 1 to about 7;
• r is an integer from 0 to about 3;
• s is an integer from 0 to about 3;
• m is an integer from 2 to about 10;
• and
• t is an integer from 1 to about 10.

A method to modify a substrate comprising the step of applying a compound of formula:

• L-(D-T-C(R1)(XP)CHR2GR3C(═O)R4)m
• wherein
• L is a linking group comprising
• a formula according to structure (I):
• A, B and J form a ring, wherein A and J are C═O;
• B is NR11;
• R11 is a hydrogen atom, an alkyl group, an aryl group or denotes a bond;
• D is CR6R7;
• T is (—CH2—)x, (—CH2CH2—O—)x, (—CH2CH2CH2—O—)x, (—CH2CH2CH2CH2—O—)x or forms a bond;
• R1 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group;
• X is O, S, or NR8R9;
• P is a hydrogen atom or a protecting group, with the proviso that P is absent when X is NR8R9;
• R2 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group;
• G is —C(═O)O—, —O—, —NHC(═O) O—, —NHC(═O)S—, —SO2—, —CONH—, —NHCONH—, —NHC(═S)NH—, —NR10—, —SO2NH—, —C(═N)—, —C(═O)— or —(CH2)t—O—;
• R3 and R4 are each independently an alkyl, aryl, arylalkyl, heteroaryl, or an heteroarylalkyl group or optionally, R3 and R4 can be tethered together via (—CH2—)q, (—CH2—)rC═O(—CH2—)s, (—CH2—)rS(—CH2—)s, (—CH2—)rS═O(—CH2—)s or (—CH2—)rS(O)2(—CH2—)s, (—CH2—)rNR(—C-H2—)s;
• R10 is a hydrogen atom or an alkyl, aryl or arylalkyl group;
• R6 and R7 are each independently a hydrogen atom, an alkyl, aryl, arylalkyl, heteroaryl or heteroarylalkyl group;
• R8 and R9 are each independently a hydrogen atom, an alkyl, aryl, or arylalkyl group;
• R is a hydrogen atom, an alkyl or an aryl group;
• q is an integer from 1 to about 7;
• r is an integer from 0 to about 3;
• s is an integer from 0 to about 3;
• m is an integer from 2 to about 10;
• t is an integer from 1 to about 10;
• and
• x is an integer from 1 to about 500 to the surface of the substrate, such that the substrate surface is modified.

A method to modify a substrate comprising the step of applying a compound of formula:

• L-(T-C(R1)(XP)CHR2GR3C(═O)R4)m
• wherein
• L is a linking group comprising
• a formula according to structure (I):
• A, B and J form a ring, wherein A and J are C═O;
• B is NR11;
• R11 is a hydrogen atom, an alkyl group, an aryl group or denotes a bond with T;
• T is (—CH2—)x, (—CH2CH2—O—)x, (—CH2CH2CH2—O—)x, (—CH2CH2CH2CH2—O—)x or forms a bond;
• R1 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group;
• X is O, S, or NR8R9;
• P is a hydrogen atom or a protecting group, with the proviso that P is absent when X is NR8R9;
• R2 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group;
• G is —C(═O)O—, —O—, —NHC(═O)O—, —NHC(═O)S—, —CONH—, —NHCONH—, —NHC(═S)NH—, —NR 10—, —SO2NH—, —C(═N)—, —C(═O)— or —(CH2)t—O—;
• R3 and R4 are each independently an alkyl, aryl, arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally, R3 and R4 can be tethered together via (—CH2—)q, (—CH2—)rC═O(—CH2—)s, (—CH2—)rS(—CH2—)s, (—CH2—)rS═O(—CH2—)s or (—CH2—)rS(O)2(—CH2—)s, (—CH2—)rNR(—CH2—)s;
• R10 is a hydrogen atom or an alkyl, aryl or arylalkyl group;
• R8 and R9 are each independently a hydrogen atom, an alkyl, aryl, or arylalkyl group;
• R is a hydrogen atom, an alkyl or aryl group;
• q is an integer from 1 to about 7;
• r is an integer from 0 to about 3;
• s is an integer from 0 to about 3;
• m is an integer from 2 to about 10;
• t is an integer from 1 to about 10;
• and
• x is an integer from 1 to about 500 to the surface of the substrate, such that the substrate surface is modified.

A method to modify a substrate comprising the step of applying a compound of formula:

• L-(GTZR3C(═O)R4)m wherein
• L is a linking group comprising
• a formula according to structure (I):
• A, B and J form a ring, wherein A and J are C═;
• B is NR11;
• R11 is a hydrogen atom, an alkyl group, an aryl group or denotes a bond;
• T is (—CH2—)x, (—CH2CH2—O—)x, (—CH2CH2CH2—O—)x, (—CH2CH2CH2CH2—O—)x or forms a bond;
• G is —C(═O) O—, —NHC(═O) O—, —NHC(═O)S—, —CONH—, —NHCONH—, —NHC(═S)NH—, —C(═N)—, —C(═O)— or —(CH2)t—O—;
• Z is C═O, COO, or CONH when T is (—CH2—)x;
• R3 and R4 are each independently an alkyl, aryl, arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally, R3 and R4 can be tethered together via (—CH2—)q, (—CH2—)rC═O(—CH2—)s, (—CH2—)rS(—CH2—)s, (—CH2—)rS═O(—CH2—)s or (—CH2—)rS(O)2(—CH2—)s, (—CH2—)rNR(—CH2—)s;
• R is a hydrogen atom or an alkyl or aryl group;
• q is an integer from 1 to about 7;
• r is an integer from 0 to about 3;
• s is an integer from 0 to about 3;
• m is an integer from 2 to about 10;
• t is an integer from 1 to about 10;
• and
• x is an integer from 1 to about 500 to the surface of the substrate, such that the substrate surface is modified.

A method to modify a substrate comprising the step of applying a compound of formula:

• L-(TGQR3C(═O)R4)m
• wherein
• L is a linking group comprising
• a formula according to structure (I):
• A, B and J form a ring, wherein A and J are C═O;
• B is NR11;
• R11 is a hydrogen atom, an alkyl group, an aryl group or denotes a bond with T;
• T is (—CH2—)x, (—CH2CH2—O—)x, (—CH2CH2CH2—O—)x, (—CH2CH2CH2CH2—O—)x or forms a bond;
• G is, —C(═O) O—, —O—, —NHC(═O)O—, —NHC(═O)S—, —SO2—, —CONH—, —NHCONH—, —NHC(═S)NH—, —NR10—, —SO2NH—, —C(═N)—, —C(═O)— or —(CH2)t—O—;
• Q is (—CH2—)p, (—CH2CH2—O—)p, (—CH2CH2CH2—O—)p or (—CH2CH2CH2CH2—O—)p;
• R3 and R4 are each independently an alkyl, aryl, arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally, R3 and R4 can be tethered together via (—CH2—)q, (—CH2—)rC═O(—CH2—)s, (—CH2—)rS(—CH2—)s, (—CH2—)rS═O(—CH2—)s or (—CH2—)rS(O)2(—CH2—)s, (—CH213 )rNR(—CH2—)s;
• R10 is a hydrogen atom or an alkyl, aryl, or an arylalkyl group;
• R is a hydrogen atom or an alkyl or aryl group;
• q is an integer from 1 to about 7;
• r is an integer from 0 to about 3;
• s is an integer from 0 to about 3;
• m is an integer from 2 to about 10;
• p is an integer from 1 to about 10;
• t is an integer from 1 to about 10;
• and
• x is an integer from 1 to about 500 to the surface of the substrate, such that the substrate surface is modified.

A method to modify a substrate comprising the step of applying a compound of formula:

• L-(—CH2—)xxC(R1)(GR3C(═O)R4)m
• wherein
• L is a linking group comprising
• a formula according to structure (I):
• A, B and J form a ring, wherein A and J are C═O;
• B is NR11;
• R11 is a hydrogen atom, an alkyl group, an aryl group or denotes a bond;
• R1 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl, or aryloxyaryl group;
• each G is —C(═O) O—, —O—, —NHC(═O)O—, —NHC(═O)S—, —SO2—, —CONH—, —NHCONH—, —NHC(═S)NH—, —NR10—, —SO2NH—, —C(═N)—, —C(═O)— or —(CH2)t—O—;
• each R3 and R4 are each independently an alkyl, aryl, arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally, R3 and R4 can be tethered together via (—CH2—)q, (—CH2—)rC═O(—CH2—)s, (—CH2—)rS(—CH2—)s, (—CH2—)rS═O(—CH2—)s or (—CH2—)rS(O)2(—CH2—)s, (—CH2—)rNR(—CH2—)s;
• each R10 is a hydrogen atom or an alkyl, aryl, or an arylalkyl group;
• each R is a hydrogen atom or an alkyl or aryl group;
• each q is an integer from 1 to about 7;
• each r is an integer from 0 to about 3;
• each s is an integer from 0 to about 3;
• m is an integer from 2 to about 10;
• each t is an integer from 1 to about 10;
• and
• xx is an integer from 1 to about 10 to the surface of the substrate, such that the substrate surface is modified.

A method to modify a substrate comprising the step of applying a compound of formula:

• L-(—C(R1)(XP)CHR2GR3C(═O)R4)m
• wherein
• L is a linking group comprising
• a formula according to structure (I):
• A, B and J form a ring, wherein A and J are C═O;
• B is NR11;
• R11 is a hydrogen atom, an alkyl group, an aryl group or denotes a bond;
• R1 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group;
• X is O, S, or NR8R9;
• P is a hydrogen atom or a protecting group, with the proviso that P is absent when X is NR8R9;
• R2 is a hydrogen atom, an alkyl, alkyloxyalkyl, aryl, aryloxyalkyl or aryloxyaryl group;
• G is —C(═O)O—, —O—, —NHC(═O)O—, —NHC(═O)S—, —SO2—, —CONH—, —NHCONH—, —NHC(═S)NH—, —NR10 —, —SO2NH—, —C(═N)—, —C(═O)— or —(CH2)t—O—;
• R3 and R4 are each independently an alkyl, aryl, arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally, R3 and R4 can be tethered together via (—CH2—)q, (—CH2—)rC═O(—CH2—)s, (—CH2—)rS(—CH2—)s, (—CH2—)rS═O(—CH2—)s or (—CH2—)rS(O)2(—CH2—)s, (—CH2—)rNR(—CH2—)s;
• R8 and R9 are each independently a hydrogen atom, an alkyl, aryl, or arylalkyl group;
• R10 is a hydrogen atom or an alkyl, aryl, or an arylalkyl group;
• R is a hydrogen atom, an alkyl or an aryl group;
• q is an integer from 1 to about 7;
• r is an integer from 0 to about 3;
• s is an integer from 0 to about 3;
• m is an integer from 2 to about 10;
• and
• t is an integer from 1 to about 10 to the surface of the substrate, such that the substrate surface is modified.

A method to modify a substrate comprising the step of applying a compound of formula:

• L-(GR3C(═O)R4)m;
• wherein
• L is a linking group comprising
• a formula according to structure (I):
• A, B and J form a ring, wherein A and J are C═O;
• B is NR11;
• R11 is a hydrogen atom, an alkyl group, an aryl group or denotes a bond;
• G is —C(═O) O—, —NHC(═O)O—, —NHC(═O)S—, —CONH—, —NHCONH—, —NHC(═S)NH—, —C(═N)—, —C(═O)— or —(CH2)t—O—;
• R3 and R4 are each independently an alkyl, aryl, arylalkyl, heteroaryl, or an heteroarylalkyl group, or optionally, R3 and R4 can be tethered together via (—CH2—)q, (—CH2—)rC═O(—CH2—)s, (—CH2—)rS(—CH2—)s, (—CH2—)rS═O(—CH2—)s or (—CH2—)rS(O)2(—CH2—)s, (—CH2—)rNR(—CH2—)s;
• R is a hydrogen atom, an alkyl or an aryl group;
• q is an integer from 1 to about 7;
• r is an integer from 0 to about 3;
• s is an integer from 0 to about 3;
• m is an integer from 2 to about 10;
• and
• t is an integer from 1 to about 10 to the surface of the substrate, such that the substrate surface is modified.