POLYMERS FOR SPECIALTY APPLICATIONS
The invention relates to ring-opening metathesis polymerization (ROMP) reactions of making polymers suitable for the electronic industry. Particularly, the invention relates to novel polymers with low dielectric constant (D k ) and low dielectric loss (D f ) suited for smaller, lighter, higher speeds and higher frequency transmission electronic products. Such polymers can be used in a variety of materials and composites of the printed circuit board (PCB) industry.
1 . A polymer having a dielectric constant D k <3 at 1 to 100 GHz and a dielectric loss D f <0.01 at 1 to 100 GHz, synthesized by ring opening metathesis reactions comprising at least one monomer of Formulae (I), (II), and (III), optionally an olefin of Formula (IV), and at least one metal carbene olefin metathesis catalyst,
z is 0, 1, 2, or 3;
R a is H, optionally substituted linear or branched C 1-24 alkyl, optionally substituted linear or branched C 2-24 alkenyl, halogen, —C(O)R f , —CH 2 —C(O)R f , —OR g , —CH 2 —OR g , CN, NO 2 , —CF 3 , —P(O)(OH) 2 , —OP(O)(OH) 2 , optionally substituted heterocycle, —CH 2 -(optionally substituted heterocycle), optionally substituted C 3-10 cycloalkyl, —CH 2 -(optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 aryl, —CH 2 -(optionally substituted C 5-24 aryl), optionally substituted C 3-8 cycloalkenyl, or —CH 2 -(optionally substituted C 3-8 cycloalkenyl);
R b is H, optionally substituted linear or branched C 1-24 alkyl, optionally substituted linear or branched C 2-24 alkenyl, halogen, —C(O)R f , —CH 2 —C(O)R f , —OR g , —CH 2 —OR g , CN, NO 2 , —CF 3 , —P(O)(OH) 2 , —OP(O)(OH) 2 , optionally substituted heterocycle, —CH 2 -(optionally substituted heterocycle), optionally substituted C 3-10 cycloalkyl, —CH 2 -(optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 aryl, —CH 2 -(optionally substituted C 5-24 aryl), optionally substituted C 3-8 cycloalkenyl, or —CH 2 -(optionally substituted C 3-8 cycloalkenyl);
R c is H, optionally substituted linear or branched C 1-24 alkyl, optionally substituted linear or branched C 2-24 alkenyl, halogen, —C(O)R f , —CH 2 —C(O)R f , —OR g , —CH 2 —OR g , CN, NO 2 , —CF 3 , —P(O)(OH) 2 , —OP(O)(OH) 2 , optionally substituted heterocycle, —CH 2 -(optionally substituted heterocycle), optionally substituted C 3-810 cycloalkyl, —CH 2 -(optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 aryl, —CH 2 -(optionally substituted C 5-24 aryl), optionally substituted C 3-8 cycloalkenyl, —CH 2 -(optionally substituted C 3-8 cycloalkenyl), —C(R h )(R i )COOR j , —C(R h )(R i )C(O)H, —C(R h )(R i )C(O)R k , —C(R h )(R i )CR l (OR m )(OR n ), —C(R h )(R i )C(O)NR c R 42 , —C(R h )(R i )C(O)NR o OR n , or together with R d can form a polycyclic ring;
R d is H, optionally substituted linear or branched C 1-24 alkyl, optionally substituted linear or branched C 2-24 alkenyl, halogen, —C(O)R f , —CH 2 —C(O)R f , —OR g , —CH 2 —OR g , CN, NO 2 , —CF 3 , —P(O)(OH) 2 , —OP(O)(OH) 2 , optionally substituted heterocycle, —CH 2 -(optionally substituted heterocycle), optionally substituted C 3-10 cycloalkyl, —CH 2 -(optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 aryl, —CH 2 -(optionally substituted C 5-24 aryl), optionally substituted C 3-8 cycloalkenyl, —CH 2 -(optionally substituted C 3-8 cycloalkenyl), —C(R h )(R i )COOR j , —C(R h )(R i )C(O)H, —C(R h )(R i )C(O)R k , —C(R h )(R i )CR l (OR m )(OR n ), —C(R h )(R i )C(O)NR o R p , —C(R h )(R i )C(O)NR o OR n , or together with R c can form a polycyclic ring;
each R s is independently optionally substituted linear or branched C 1-24 alkyl, optionally substituted linear or branched C 2-24 alkenyl, halogen, —C(O)R f , —CH 2 —C(O)R f , —OR g , —CH 2 —OR g , CN, NO 2 , —CF 3 , —P(O)(OH) 2 , —OP(O)(OH) 2 , optionally substituted heterocycle, —CH 2 -(optionally substituted heterocycle), optionally substituted C 3-10 cycloalkyl, —CH 2 -(optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 aryl, —CH 2 -(optionally substituted C 5-24 aryl), optionally substituted C 3-8 cycloalkenyl, —CH 2 -(optionally substituted C 3-8 cycloalkenyl), —C(R h )(R i )COOR j , —C(R h )(R i )C(O)H, —C(R h )(R i )C(O)R k , —C(R h )(R i )CR l (OR m )(OR n ), —C(R h )(R i )C(O)NR o R p , or —C(R h )(R i )C(O)NR o OR n ;
t is 0, 1, 2, 3, 4, 5, or 6;
R f is OH, OR k , NR g R h , optionally substituted linear or branched C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R g is H, optionally substituted linear or branched C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, optionally substituted linear or branched C 2-6 alkenyl, —C(O)-(optionally substituted linear or branched C 2-6 alkenyl), or optionally substituted C 3-8 cycloalkenyl;
R h is H, optionally substituted linear or branched C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R i is H, optionally substituted linear or branched C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R j is H, optionally substituted linear or branched C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R k is optionally substituted linear or branched C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R l is H, optionally substituted linear or branched C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R m is H, optionally substituted linear or branched C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R n is H, optionally substituted linear or branched C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R o is H, optionally substituted linear or branched C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl; and
R p is H, optionally substituted linear or branched C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl.
2 . The polymer according to claim 1 , wherein:
R a is H, optionally substituted linear or branched C 1-6 alkyl, optionally substituted linear or branched C 2-6 alkenyl, halogen, —C(O)R f , —CH 2 —C(O)R f , —OR g , —CH 2 —OR g , CN, NO 2 , —CF 3 , —P(O)(OH) 2 , —OP(O)(OH) 2 , optionally substituted heterocycle, —CH 2 -(optionally substituted heterocycle), optionally substituted C 5-7 cycloalkyl, —CH 2 -(optionally substituted C 5-7 cycloalkyl), optionally substituted C 6-10 aryl, —CH 2 -(optionally substituted C 6-10 aryl), optionally substituted C 3-8 cycloalkenyl, or —CH 2 -(optionally substituted C 3-8 cycloalkenyl);
R b is H, optionally substituted linear or branched C 1-6 alkyl, optionally substituted linear or branched C 2-6 alkenyl, halogen, —C(O)R f , —CH 2 —C(O)R f , —OR g , —CH 2 —OR g , CN, NO 2 , —CF 3 , —P(O)(OH) 2 , —OP(O)(OH) 2 , optionally substituted heterocycle, —CH 2 -(optionally substituted heterocycle), optionally substituted C 5-7 cycloalkyl, —CH 2 -(optionally substituted C 5-7 cycloalkyl), optionally substituted C 6-10 aryl, —CH 2 -(optionally substituted C 6-10 aryl), optionally substituted C 3-8 cycloalkenyl, or —CH 2 -(optionally substituted C 3-8 cycloalkenyl);
t is 0;
R f is OH, OR k , NR g R h , optionally substituted linear or branched C 1-6 alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C 6-10 aryl, or optionally substituted C 3-8 cycloalkenyl;
R g is H, optionally substituted linear or branched C 1-6 alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C 6-10 aryl, optionally substituted linear or branched C 2-6 alkenyl, —C(O)-(optionally substituted linear or branched C 2-6 alkenyl), or optionally substituted C 3-8 cycloalkenyl;
R h is H, optionally substituted linear or branched C 1-6 alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C 6-10 aryl, or optionally substituted C 3-8 cycloalkenyl;
R k is optionally substituted linear or branched C 1-6 alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C 6-10 aryl, or optionally substituted C 3-8 cycloalkenyl;
z is 2;
R c is H, optionally substituted linear or branched C 1-6 alkyl, optionally substituted linear or branched C 2-6 alkenyl, halogen, —C(O)R f , —CH 2 —C(O)R f , —OR g , CN, NO 2 , —CF 3 , —P(O)(OH) 2 , —OP(O)(OH) 2 , optionally substituted heterocycle, —CH 2 -(optionally substituted heterocycle), optionally substituted C 5-7 cycloalkyl, —CH 2 -(optionally substituted C 5-7 cycloalkyl), optionally substituted C 6-10 aryl, —CH 2 -(optionally substituted C 6-10 aryl), optionally substituted C 3-8 cycloalkenyl, or —CH 2 -(optionally substituted C 3-8 cycloalkenyl); and
R d is H, optionally substituted linear or branched C 1-6 alkyl, optionally substituted linear or branched C 2-6 alkenyl, halogen, —C(O)R f , —CH 2 —C(O)R f , —OR g , CN, NO 2 , —CF 3 , —P(O)(OH) 2 , —OP(O)(OH) 2 , optionally substituted heterocycle, —CH 2 -(optionally substituted heterocycle), optionally substituted C 5-7 cycloalkyl, —CH 2 -(optionally substituted C 5-7 cycloalkyl), optionally substituted C 5-24 aryl, —CH 2 -(optionally substituted C 6-10 aryl), optionally substituted C 3-8 cycloalkenyl, or —CH 2 -(optionally substituted C 3-8 cycloalkenyl).
3 . The polymer according to claim 1 , wherein:
R a is optionally substituted linear or branched C 2-24 alkenyl, optionally substituted linear or branched C 1-24 alkyl, or optionally substituted C 5-24 aryl;
z is 2;
R b is optionally substituted linear or branched C 1-24 alkyl, —CH 2 —OR g , —CH 2 -(optionally substituted heterocycle), —C(O)R f , optionally substituted heterocycle, spiro optionally substituted heterocycle, —CH 2 -(optionally substituted C 5-24 aryl), or —CH 2 —OR g ;
R g is H, optionally substituted linear or branched C 1-24 alkyl, —C(O)-(optionally substituted linear or branched C 2-6 alkenyl), or optionally substituted C 5-24 aryl;
R f is OH;
R c is H; and
R d is optionally substituted linear or branched C 1-24 alkyl, or —CH 2 -(optionally substituted heterocycle).
4 . The polymer according to claim 1 , wherein the at least one monomer of Formula (I) has the structure wherein: R a is
and t=0; the at least one monomer of Formula (II) has the structure wherein: R b is
and t=0; the at least one monomer of Formula (III) has the structure wherein z is 1 or 2; and the at least one olefin of Formula (IV) has the structure wherein: R c is
and R d is
5 . The polymer according to claim 1 , wherein: the at least one monomer of Formula (I) is
the at least one monomer of Formula II is
the at least one monomer of Formula (III) is
and the at least one olefin of Formula (IV) is
6 . The polymer according to claim 1 , wherein: the at least one monomer of Formula (I) is
the at least one monomer of Formula (II) is
the at least one monomer of Formula (III) is
and the at least one olefin of Formula (IV) is
7 . The polymer according to any of claims 1 - 6 , wherein the at least one metal carbene olefin metathesis catalyst has the structure of Formula (1):
wherein:
M is ruthenium;
L 1 , L 2 , and L 3 are independently neutral electron donor ligands;
n is 0 or 1;
m is 0, 1, or 2;
k is 0 or 1;
X 1 and X 2 are independently anionic ligands; and
R 1 and R 2 are independently hydrogen, optionally substituted hydrocarbyl, optionally substituted heteroatom-containing hydrocarbyl; or R 1 and R 2 are linked together to form one or more cyclic groups.
8 . The polymer according to any of claims 1 - 6 , wherein the at least one metal carbene olefin metathesis catalyst has the structure of Formula (2):
wherein:
L 1 is an independently neutral electron donor ligand;
X 1 and X 2 are independently anionic ligands;
W is O, halogen, NR 33 , or S;
R 19 is H, optionally substituted C 1-24 alkyl, —C(R 34 )(R 35 )COOR 36 , —C(R 34 )(R 35 )C(O)H, —C(R 34 )(R 35 )C(O)R 37 , —C(R 34 )(R 35 )CR 38 (OR 39 )(OR 40 ), —C(R 34 )(R 35 )C(O)NR 41 R 42 , —C(R 34 )(R 35 )C(O)NR 41 OR 40 , —C(O)R 25 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or when W is NR 33 , then R 19 together with R 33 can form an optionally substituted heterocyclic ring or when W is halogen then R 19 is nil;
R 20 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 21 can form a polycyclic ring;
R 21 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 20 or together with R 22 can form a polycyclic ring;
R 22 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 21 or together with R 23 can form a polycyclic ring;
R 23 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 22 can form a polycyclic ring;
R 24 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 25 is OH, OR 30 , NR 27 R 28 , optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 26 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 27 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 28 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 29 is H, optionally substituted C 1-24 alkyl, OR 26 , —NR 27 R 28 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 30 is optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 31 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 33 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 34 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 35 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 36 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 37 is optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 38 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 39 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 40 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 41 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 42 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl; and
x is 1 or 2.
9 . The polymer according to claim 7 or claim 8 , wherein L 1 is
wherein
X and Y are independently C, CR 3a , N, O, S, or P;
Q 1 , Q 2 , R 3 , R 3a , and R 4 are independently hydrogen optionally substituted hydrocarbyl, optionally substituted heteroatom-containing hydrocarbyl;
p is 0, when X is O or S, p is 1, when X is N, P, or CR 3a , and p is 2, when X is C; and
q is 0, when Y is O or S, q is 1, when Y is N, P, or CR 3a , and q is 2, when X is C.
10 . The polymer according to claim 7 or claim 8 , wherein L 1 is
wherein:
Q is a two-atom linkage having the structure —[CR 11 R 12 ] s —[CR 13 R 14 ] t — or —[CR 11 ═CR 13 ]—, wherein R 11 , R 12 , R 13 , and R 14 are independently hydrogen, optionally substituted hydrocarbyl, optionally substituted heteroatom-containing hydrocarbyl;
s and t are independently 1 or 2; or
any two of R 11 , R 12 , R 13 , and R 14 are optionally linked together and can form an optionally substituted, saturated or unsaturated polycyclic ring structure.
11 . The polymer according to claim 7 or claim 8 , wherein L 1 is
wherein:
Z is N or CR 32 ;
R 1 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 2 can form a spiro compound, or together with R 3 or together with R 4 can form a polycyclic ring;
R 2 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 1 can form a spiro compound, or together with R 3 or together with R 4 can form a polycyclic ring;
R 3 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 2 or together with R 1 can form a polycyclic ring or together with R 4 can form a spiro compound;
R 4 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 3 can form a spiro compound, or together with R 2 or together with R 1 can form a polycyclic ring;
R 5 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 6 can form an optionally substituted polycyclic ring;
R 6 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 5 or together with R 7 can form an optionally substituted polycyclic ring;
R 7 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl optionally substituted C 3-8 cycloalkenyl, or together with R 6 or together with R 8 can form an optionally substituted polycyclic ring;
R 8 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 7 or together with R 9 can form an optionally substituted polycyclic ring;
R 9 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 8 can form an optionally substituted polycyclic ring;
R 10 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 11 can form an optionally substituted polycyclic ring;
R 11 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 10 or together with R 12 can form an optionally substituted polycyclic ring;
R 12 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 11 or together with R 13 can form an optionally substituted polycyclic ring;
R 13 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 14 or together with R 12 can form an optionally substituted polycyclic ring;
R 14 is H, optionally substituted C 1-24 alkyl, halogen, —C(O)R 25 , —OR 26 , CN, —NR 27 R 28 , NO 2 , —CF 3 , —S(O) x R 29 , —P(O)(OH) 2 , —OP(O)(OH) 2 , —SR 31 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 13 can form a polycyclic ring;
R 32 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 25 is OH, OR 30 , NR 27 R 28 , optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 26 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 27 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 28 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 29 is H, optionally substituted C 1-24 alkyl, OR 26 , —NR 27 R 28 , optionally substituted heterocycle, optionally substituted C 3-10 cycloalkyl, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 30 is optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl;
R 31 is H, optionally substituted C 1-24 alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, or optionally substituted C 3-8 cycloalkenyl; and
x is 1 or 2.
12 . The polymer according to any of claims 7 - 11 , wherein the ring opening metathesis reactions comprise at least one monomer of Formula (I), and at least one monomer of Formula (II), and at least one metal carbene olefin metathesis catalyst of Formula (1), Formula (2), or mixtures thereof.
13 . The polymer according to any of claims 7 - 11 , wherein the ring opening metathesis reactions comprise at least one monomer of Formula (I), and at least one monomer of Formula (II), and at least one olefin of Formula (IV), and at least one metal carbene olefin metathesis catalyst of Formula (1), Formula (2), or mixtures thereof.
14 . The polymer according to any of claims 7 - 11 , wherein the ring opening metathesis reactions comprise at least one monomer of Formula (I), and at least one monomer of Formula (II), and at least one monomer of Formula (III), and at least one metal carbene olefin metathesis catalyst of Formula (1), Formula (2), or mixtures thereof.
15 . The polymer according to any of claims 7 - 11 , wherein the ring opening metathesis reactions comprise at least one monomer of Formula (II), and at least one monomer of Formula (III), and at least one olefin of Formula (IV), and at least one metal carbene olefin metathesis catalyst of Formula (1), Formula (2), or mixtures thereof.
16 . The polymer according to any of claims 7 - 11 , wherein the ring opening metathesis reactions comprise at least one monomer of Formula (I), and at least one monomer of Formula (III), and at least one metal carbene olefin metathesis catalyst of Formula (1), Formula (2), or mixtures thereof.
17 . An article of manufacture, comprising the polymer according to any of claims 1 - 16 .
18 . The article of manufacture of claim 17 , wherein the article of manufacture is selected from the group consisting of a prepreg, a fiber composite laminate, a solvent based coating, a melt-extruded part, a film, and a liquid compound.
19 . The polymer according to any of claims 1 - 16 , wherein the polymer is crosslinked optionally in the presence of free-radical initiators, cationic initiators, other curative agents, or mixtures thereof.