Flame retardant vinyl addition polycycloolefinic polymers
The present invention relates to certain vinyl addition polymers encompassing polycycloolefinic monomers and a certain of olefinic monomers having thermally labile functional group. More specifically, the present invention relates to vinyl addition polymers under mass polymerization conditions of a series of functionalized norbornene-type monomers and at least one other olefinic monomer containing a thermally labile functional group such as, ether, acetal, ester, and the like. This invention also relates to reaction compositions containing a series of functionalized norbornene-type monomers and at least one other olefinic monomer containing a thermally labile functional group such as, ether, acetal, ester, and the like, which undergo vinyl addition polymerization to produce materials which are useful as flame retardant materials having a variety of applications.
1. A polymer comprising one or more first type of repeating units represented by formula (IA), said first type of repeating unit is derived from a monomer of formula (I):
wherein:
denotes a place of bonding with another repeat unit;
a is an integer 0, 1 or 2;
R 1 , R 2 , R 3 and R 4 are the same or different and each independently of one another is selected from hydrogen, linear or branched (C 1 -C 16 )alkyl, hydroxy(C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 3 -C 6 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 2 -C 6 )alkoxy(C 1 -C 2 )alkyl, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 1 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, and (C 1 -C 6 )acyloxy, where each of the aforementioned substituents are optionally substituted with a group selected from halogen or hydroxy; and
at least one second type of repeat unit derived from one of the monomers selected from the group consisting of:
a monomer of formula (II):
wherein:
at least one of R 5 , R 6 , R 7 and R 8 independently represents a group of formula (A):
wherein:
Z is selected from —CO—O—, —O—CO— and —O—CO—O—;
R 9 and R 10 are the same or different and each independently of one another is selected from linear or branched (C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl and perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl;
R 11 is selected from substituted or unsubstituted (C 1 -C 6 )alkylene, (C 6 -C 10 )arylene (C 6 -C 10 )aryl(C 2 -C 6 )alkylene and (C 2 -C 6 )alkyl(C 6 -C 10 )arylene;
remaining one or more of R 5 , R 6 , R 7 and R 8 independently represents hydrogen, linear or branched (C 1 -C 12 )alkyl, hydroxy(C 1 -C 12 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 3 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, and (C 1 -C 6 )acyloxy and halogen;
a monomer of formula (III):
wherein:
b is an integer from 2 to 6;
R 12 , R 13 , R 16 and R 17 are the same or different and each independently of one another is selected from hydrogen, linear or branched (C 1 -C 16 )alkyl, hydroxy(C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 3 -C 6 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 2 -C 6 )alkoxy(C 1 -C 2 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, and (C 1 -C 6 )acyloxy, where each of the aforementioned substituents are optionally substituted with a group selected from halogen or hydroxy; and
R 14 and R 15 are the same or different and each independently of one another is selected from linear or branched (C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl and perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl; and
a monomer of formula (IV):
wherein:
c is an integer from 2 to 6;
Ar is (C 6 -C 10 )aryl; and
Z, R 9 , R 10 and R 11 are as defined above.
2. The polymer of claim 1 , wherein said one or more monomers of formula (I) is having:
a is 0 or 1;
at least one of R 1 , R 2 , R 3 and R 4 is selected from hydrogen, linear or branched (C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, and perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl; and
each of the remaining R 1 , R 2 , R 3 and R 4 is hydrogen.
3. The polymer of claim 1 , wherein said one or more monomers of formula (I) is selected from the group consisting of:
bicyclo[2.2.1]hept-2-ene (NB);
norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
5-hexylbicyclo-[2.2.1]hept-2-ene (HexNB);
5-octylbicyclo[2.2.1]hept-2-ene (OctNB);
5-decylbicyclo[2.2.1]hept-2-ene (DecNB);
5-perfluorobutylbicyclo[2.2.1]hept-2-ene (C 4 F 9 NB);
5-phenethylbicyclo[2.2.1]hept-2-ene (PENB); and
2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (NBANB).
4. The polymer of claim 1 , wherein said one or more monomers of formula (I) are at least two distinct types of monomers of formula (I).
5. The polymer of claim 1 , wherein said polymer comprises one or more repeat units derived from corresponding monomers of formula (I) and a second type of repeat unit derived from a monomer of formula (II).
6. The polymer of claim 5 , wherein said second type of repeat unit derived from a monomer of formula (II) is having:
Z is —CO—O—;
R 9 and R 10 are the same or different and each independently of one another is selected from linear or branched (C 1 -C 10 )alkyl, perfluoro(C 1 -C 8 )alkyl, phenyl, naphthyl, benzyl, phenylethyl, perfluorophenyl and perfluorobenzyl;
R 11 is selected from substituted or unsubstituted (C 2 -C 4 )alkylene and phenylene;
remaining one or more of R 5 , R 6 , R 7 and R 8 independently represents hydrogen, linear or branched (C 1 -C 12 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl and perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl.
7. The polymer of claim 6 , wherein said second type of repeat unit is derived from a monomer of formula (II) selected from the group consisting of:
8. The polymer of claim 1 , wherein said polymer comprises one or more repeat units derived from corresponding monomers of formula (I) and a second type of repeat unit derived from a monomer of formula (III).
9. The polymer of claim 8 , wherein said second type of repeat unit derived from a monomer of formula (III) is having:
b is an integer from 2 to 4;
R 12 , R 13 , R 16 and R 17 are the same or different and each independently of one another is selected from hydrogen, linear or branched (C 1 -C 12 )alkyl, perfluoro(C 1 -C 8 )alkyl, (C 3 -C 7 )cycloalkyl, (C 6 -C 9 )bicycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, and di(C 1 -C 2 )alkylmaleimide(C 3 -C 6 )alkyl, where each of the aforementioned substituents are optionally substituted with a group selected from halogen or hydroxy; and
R 14 and R 15 are the same or different and each independently of one another is selected from linear or branched (C 1 -C 12 )alkyl, perfluoro(C 1 -C 8 )alkyl, (C 3 -C 7 )cycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl and perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl.
10. The polymer of claim 9 , wherein said second type of repeat unit is derived from a monomer of formula (III) selected from the group consisting of:
11. The polymer of claim 1 , wherein said polymer comprises one or more repeat units derived from corresponding monomers of formula (I) and a second type of repeat unit derived from a monomer of formula (IV).
12. The polymer of claim 8 , wherein said second type of repeat unit derived from a monomer of formula (III) is having:
c is an integer from 2 to 4;
Ar is phenyl or naphthyl; and
Z is —CO—O—;
R 9 and R 10 are the same or different and each independently of one another is selected from linear or branched (C 1 -C 10 )alkyl, perfluoro(C 1 -C 8 )alkyl, phenyl, naphthyl, benzyl, phenylethyl, perfluorophenyl and perfluorobenzyl;
R 11 is selected from substituted or unsubstituted (C 2 -C 4 )alkylene and phenylene;
remaining one or more of R 5 , R 6 , R 7 and R 8 independently represents hydrogen, linear or branched (C 1 -C 12 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl and perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl.
13. The polymer of claim 12 , wherein said second type of repeat unit is derived from a monomer of formula (IV) selected from the group consisting of:
14. A reaction composition comprising:
one or more monomers of formula (I):
wherein:
a is an integer 0, 1 or 2;
R 1 , R 2 , R 3 and R 4 are the same or different and each independently of one another is selected from hydrogen, linear or branched (C 1 -C 16 )alkyl, hydroxy(C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 3 -C 6 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 2 -C 6 )alkoxy(C 1 -C 2 )alkyl, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, and (C 1 -C 6 )acyloxy, where each of the aforementioned substituents are optionally substituted with a group selected from halogen or hydroxy; and
at least one second monomer selected from the group consisting of:
a monomer of formula (II):
wherein:
at least one of R 5 , R 6 , R 7 and R 8 independently represents a group of formula (A):
wherein:
Z is selected from —CO—O—, —O—CO— and —O—CO—O—;
R 9 and R 10 are the same or different and each independently of one another is selected from linear or branched (C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl and perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl;
R 11 is selected from substituted or unsubstituted (C 1 -C 6 )alkylene, (C 6 -C 10 )arylene (C 6 -C 10 )aryl(C 2 -C 6 )alkylene and (C 2 -C 6 )alkyl(C 6 -C 10 )arylene;
remaining one or more of R 5 , R 6 , R 7 and R 8 independently represents hydrogen, linear or branched (C 1 -C 12 )alkyl, hydroxy(C 1 -C 12 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 3 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, and (C 1 -C 6 )acyloxy and halogen;
a monomer of formula (III):
wherein:
b is an integer from 2 to 6;
R 12 , R 13 , R 16 and R 17 are the same or different and each independently of one another is selected from hydrogen, linear or branched (C 1 -C 16 )alkyl, hydroxy(C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 3 -C 6 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 2 -C 6 )alkoxy(C 1 -C 2 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, and (C 1 -C 6 )acyloxy, where each of the aforementioned substituents are optionally substituted with a group selected from halogen or hydroxy; and
R 14 and R 15 are the same or different and each independently of one another is selected from linear or branched (C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl and perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl; and
a monomer of formula (IV):
wherein:
c is an integer from 2 to 6;
Ar is (C 6 -C 10 )aryl; and
Z, R 9 , R 10 and R 11 are as defined above; and
an organo-transition metal compound selected from an organo-palladium or an organo-nickel compound; and
optionally a chain transfer agent.
15. The composition of claim 14 , wherein said organo-transition metal compound is an organo-palladium compound.
16. The composition of claim 15 , wherein said organo-transition compound is selected from the group consisting of:
trans-[Pd(NCMe)(OAc)(P(i-propyl) 3 ) 2 ]B(C 6 F 5 ) 4 ,
trans-[Pd(NCC(CH 3 ) 3 )(OAc)(P(i-propyl) 3 ) 2 ]B(C 6 F 5 ) 4 ,
trans-[Pd(OC(C 6 H 5 ) 2 )(OAc)(P(i-propyl) 3 ) 2 ]B(C 6 F 5 ) 4 ,
trans-[Pd(HOCH(CH 3 ) 2 )(OAc)(P(i-propyl) 3 ) 2 ]B(C 6 F 5 ) 4 ,
trans-[Pd(NCMe)(OAc)(P(cyclohexyl) 3 ) 2 ]B(C 6 F 5 ) 4 ,
Pd(OAc) 2 (P(cyclohexyl) 3 ) 2 ,
Pd(OAc) 2 (P(i-propyl) 3 ) 2 ,
Pd(OAc) 2 (P(i-propyl) 2 (phenyl)) 2 , and
trans-[Pd(NCMe)(OAc)(P(cyclohexyl) 2 (t-butyl)) 2 ]B(C 6 F 5 ) 4 , where OAc is OCOCH 3 .
17. The composition of claim 14 , wherein said one or more monomers of formula (I) is selected from the group consisting of:
bicyclo[2.2.1]hept-2-ene (NB);
norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
5-hexylbicyclo-[2.2.1]hept-2-ene (HexNB);
5-octylbicyclo[2.2.1]hept-2-ene (OctNB);
5-decylbicyclo[2.2.1]hept-2-ene (DecNB);
5-perfluorobutylbicyclo[2.2.1]hept-2-ene (C 4 F 9 NB);
5-phenethylbicyclo[2.2.1]hept-2-ene (PENB); and
2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (NBANB).
18. The composition of claim 14 , wherein said monomer of formula (II) is selected from the group consisting of:
2-methylbut-3-en-2-yl bicyclo[2.2.1]hept-5-ene-2-carboxylate;
2-methylpent-4-en-2-yl bicyclo[2.2.1]hept-5-ene-2-carboxylate;
2-methylhex-5-en-2-yl bicyclo[2.2.1]hept-5-ene-2-carboxylate;
2,5-dimethylhept-6-en-2-yl bicyclo[2.2.1]hept-5-ene-2-carboxylate;
2,6-dimethyloct-7-en-2-yl bicyclo[2.2.1]hept-5-ene-2-carboxylate;
3,5,7-trimethylnon-8-en-3-yl bicyclo[2.2.1]hept-5-ene-2-carboxylate;
1,1,1-trifluoro-6-methyl-2-(trifluoromethyl)oct-7-en-2-yl 3-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate; and
2,6-dimethyloct-7-en-2-yl 3,3-dimethylbicyclo[2.2.1]hept-5-ene-2-carboxylate.
19. The composition of claim 14 , wherein said monomer of formula (III) is selected from the group consisting of:
5,5′-((propane-2,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(bicyclo[2.2.1]hept-2-ene);
5,5′-((butane-2,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(bicyclo[2.2.1]hept-2-ene);
5,5′-((pentane-3,3-diylbis(oxy))bis(ethane-2,1-diyl))bis(bicyclo[2.2.1]hept-2-ene);
5,5′-(((1-phenylpropane-1,1-diyl)bis(oxy))bis(ethane-2,1-diyl))bis(bicyclo[2.2.1]hept-2-ene);
5,5′-(((1-cyclohexylpropane-1,1-diyl)bis(oxy))bis(ethane-2,1-diyl))bis(bicyclo[2.2.1]hept-2-ene);
6,6′-((propane-2,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(5-methylbicyclo[2.2.1]hept-2-ene);
5,5′-(((perfluoropropane-2,2-diyl)bis(oxy))bis(ethane-2,1-diyl))bis(bicyclo[2.2.1]hept-2-ene);
5,5′-((propane-2,2-diylbis(oxy))bis(propane-3,1-diyl))bis(bicyclo[2.2.1]hept-2-ene); and
5,5′-((propane-2,2-diylbis(oxy))bis(butane-4,1-diyl))bis(bicyclo[2.2.1]hept-2-ene).
20. The composition of claim 14 , wherein said monomer of formula (IV) is selected from the group consisting of:
bis(2,6-dimethyloct-7-en-2-yl) terephthalate;
tris(2,6-dimethyloct-7-en-2-yl) benzene-1,3,5-tricarboxylate;
tetrakis(2,6-dimethyloct-7-en-2-yl) benzene-1,2,4,5-tetracarboxylate; and
tetrakis(2,6-dimethyloct-7-en-2-yl) naphthalene-2,3,6,7-tetracarboxylate.
21. The composition of claim 14 , wherein said chain transfer agent is a compound of formula (IX):
wherein
d is an integer from 0 to 4;
e is an integer from 0 to 2a+4;
each R is hydrogen, halogen, methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, substituted or unsubstituted (C 3 -C 7 )cycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aralkyl, methoxy, ethoxy, linear or branched (C 3 -C 6 )alkoxy, substituted or unsubstituted (C 3 -C 7 )cycloalkoxy, (C 6 -C 10 )aryloxy and (C 6 -C 10 )aralkyloxy.
22. A flame retardant material comprising the polymer of claim 1 .