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US 5,395,556 AGranted
Tricyanovinyl substitution process for NLO polymers
AssigneeEnichem S.p.A.
InventorsKevin J. Drost, Pushkara R. Varanasi, Kwan-Yue A. Jen, Michael A. Drzewinski
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Abstract
Base polymers devoid of non-linear optical properties exhibiting second order non-linear optical properties after the covalent attachment of tricyanovinyl groups to pendant side chains of the base polymer. Methods of preparing a polymer having second order non-linear optical properties by reacting the base polymers of the present invention with tetracyanoethylene in a basic solvent at elevated temperatures.
Claims20
A method of preparing a polymer having second order non-linear optical properties, which method comprises the steps of:
- reacting a base polymer having pendant side chains, said base polymer comprising recurring structural units represented by the formula:
- ##STR30## with tetracyanoethylene in a basic solvent at a temperature between about 0.degree. C. and about 150.degree. C., so that R.sub.7 of said pendant side chains is tricyanovinylated;
- and
- recovering the resulting polymer having pendant tricyanovinylated side chains;
- wherein R.sub.1 and R.sub.3 are monomeric subunits independently selected from the group consisting of acrylate, imide, amide, acrylamide, styrene, vinyl halide, acrylonitrile, vinyl alcohol, vinyl acetate, polyester, polyphenylene ether, polyether ketone, polyether etherketone, acid anhydride, ethylene, propylene, isobutylene, isoprene and polycarbonate monomeric subunits, wherein each R.sub.1 subunit includes a functional group through which said side chains may be attached;
- the ratio of a to b is between about 1:99 and about 50:50;
- D comprises a first electron donating group capable of releasing electrons into said pendant side chains;
- p is zero or one;
- R.sub.2 is a straight-chained or branched alkyl, alkoxy, alkylthio or alkylamino group containing from one to ten carbon atoms attached to said monomeric subunit at said functional group, with the proviso that when p is zero, R.sub.2 is attached to said functional group by an alkyl moiety and R.sub.2 is an alkoxy, alkylthio or alkylamino group;
- each Ar comprises an aromatic substituent independently selected from the group consisting of six-membered aromatic rings, five-membered heteroaromatic rings, fused ring systems containing at least one six-membered aromatic ring and fused ring systems containing at least one five-membered heteroaromatic ring having one heteroatom selected from the group consisting of O, N, S and Se;
- R.sub.7 comprises a heteroaromatic substituent selected from the group consisting of five-membered heteroaromatic rings having one heteroatom selected from the group consisting of O, N, S and Se, fused ring systems containing at least one five-membered heteroaromatic ring having one heteroatom selected from the group consisting of O, S and Se, fused ring systems containing at least one five-membered heteroaromatic ring having two to for N heteroatoms, fused ring systems containing all five-membered heteroaromatic rings having one heteroatom selected from the group consisting of O, N, S and Se, pyrimidine and purine, so that R.sub.7 is tricyanovinylated at a ring position alpha to a heteroatom;
- B comprises a conjugated functional group, the value of n for each B is zero, one, two or three, and m is from one to nine, inclusive;
- and
- R.sub.2 or D or B are attached to a member of a heteroaromatic ring alpha to a heteroatom, and when Ar is an aromatic ring, B is attached to a member of said aromatic ring para to R.sub.2 or D or another B.
11 more elements
A method of preparing a polymer having second order non-linear optical properties, which method comprises the steps of:
- reacting a base polymer having pendant side chains, said base polymer comprising recurring structural units represented by the formula:
- ##STR31## with tetracyanoethylene in a basic solvent at a temperature between about 0.degree. C. and about 150.degree. C., so that R.sub.7 of said pendant side chains is tricyanovinylated;
- and
- recovering the resulting polymer having pendant tricyanovinylated side chains;
- wherein R.sub.1 and R.sub.3 are monomeric subunits independently selected from the group consisting of acrylate, imide, amide, acrylamide, styrene, vinyl halide, acrylonitrile, vinyl alcohol, vinyl acetate, polyester, polyphenylene ether, polyether ketone, polyether etherketone, acid anhydride, ethylene, propylene, isobutylene, isoprene and polycarbonate monomeric subunits, wherein each R.sub.1 subunit includes a functional group through which said side chains may be attached;
- the ratio of a to b is between about 1:99 and about 50:50;
- D comprises a first electron donating group selected from the group consisting of:
- --OR.sub.8, --SR.sub.8, --TeR.sub.8, --SeR.sub.8, --CH.dbd.NR.sub.4, --CH.dbd.N--NH.sub.2, --CH.dbd.N--N(R.sub.5 R.sub.6) and --CH.dbd.C[N(R.sub.5 R.sub.6)].sub.2, wherein R.sub.4 is hydrogen or an alkyl group containing up to 10 carbon atoms, R.sub.8 is an alkyl groups containing up to 6 carbon atoms and R.sub.5 and R.sub.6 are independently selected from the group consisting of hydrogen, alkyl groups containing up to 12 carbon atoms and alkyl groups containing up to 12 carbon atoms having reactive functional groups selected from the group consisting of hydroxy, ethylene, acetylene, amine, thiol, sulfonic acid and carboxylic acid, or R.sub.5 and R.sub.6 together form a cyclic group containing up to 8 carbon atoms;
- or
- D comprises a first electron donating group selected from the group consisting of:
- ##STR32## wherein E, F, G and H are members of a saturated or unsaturated five- to eight-membered ring or fused ring system which is electron donating in nature and E, F, C and H are heteroatoms independently selected from the group consisting, of O, N, S, Se and Te;
- R.sub.2 is a straight-chained or branched alkyl, alkoxy, alkylthio or alkylamino group containing from one to ten carbon atoms attached to said monomeric subunit at said functional group;
- each Ar comprises an aromatic substituent independently selected from the group consisting of six-membered aromatic rings, five-membered heteroaromatic rings, fused ring systems containing at least one six-membered aromatic ring and fused ring systems containing at least one five-membered heteroaromatic ring, having one heteroatom selected from the group consisting of O, N, S and Se;
- R.sub.7 comprises a heteroaromatic substituent selected from the group consisting of five-membered heteroaromatic rings having one heteroatom selected from the group consisting of O, N, S and Se, fused ring systems containing at least one five-membered heteroaromatic ring having one heteroatom selected from the group consisting of O, S and Se, fused ring systems containing all five-membered heteroaromatic rings having one heteroatom selected from the group consisting of O, N, S and Se, fused ring systems containing at least one five-membered heteroaromatic ring having two to four N heteroatoms, pyrimidine and purine, so that R.sub.7 is tricyanovinylated at a ring position alpha to a heteroatom;
- B comprises a conjugated functional group, the value of n for each B is 0, 1, 2 or 3, and m is from 1 to 9, inclusive;
- and
- R.sub.2 or D or B are attached to a member of a heteroaromatic ring alpha to a heteroatom, and when Ar is an aromatic ring, B is attached to a member of said aromatic ring para to R.sub.2 or D or another B.
14 more elements
Dependencies are inferred from the claim text.