Polyiptycenylene vinylene and method of making the same

1. A method for the preparation of a polymer, the method comprising:

providing a first monomer having a general formula (I):

Z—CHR 3 —Ar—CHR 4 —Z′  (I),

providing a second monomer having a general formula (XXI):

Z″—CHR 10 —Ar′—CHR 11 —Z′″  (XXI),

and reacting said first monomer and said second monomer with a basic compound in a presence of an organic solvent, whereby a polymer of general formula (IV) is obtained:

wherein:

Ar is substituted or unsubstituted, and is selected from the group consisting of triptycenylene, pentiptycenylene, and iptycenylene;

Ar′ is selected from the group consisting of arylene and heteroarylene, wherein Ar′ is unsubstituted or substituted with one or more substituents independently selected from the group consisting of C 1-20 alkyl, C 1-20 alkoxy, C 1-20 alkylsulfate, poly(ethylene oxide), oligo(ethylene oxide), aryl, and aryl-(C 1-4 alkyl), wherein said heteroarylene comprises up to 4 heteroatoms independently selected from the group consisting of oxygen, sulfur, and nitrogen;

Z, Z′, Z″, and Z′″ are independently selected from the group consisting of —S(O)R″ and —SC(S)R 0 ;

R 3 , R 4 , R 10 and R 11 are independently selected from the group consisting of hydrogen, C 1-20 alkyl, cyclic C 3-20 alkyl, aryl, alkylaryl, arylalkyl, and heterocyclyl;

R 0 is selected from the group consisting of —NR 1 R 2 , C 1-20 alkyloxy, aryloxy, alkyl, aryl, alkylaryl, arylalkyl, thioether, ester, carboxylic acid and heterocyclyl;

R 1 and R 2 are independently selected from the group consisting of C 1-20 alkyl, C 3-20 cycloalkyl, aryl, C 1-4 alkylaryl, aryl C 1-4 alkyl, and heterocyclyl, or R 1 and R 2 are linked together to form a cycle comprising 4 to 8 carbons;

R 5 is C 1-10 alkyl;

R″ is selected from the group consisting of C 1-10 alkyl and aryl;

n is from 5 to 2000; and

m is from 0 to 2000.

2. The method of claim 1 , wherein Z and Z″ are independently selected from the group consisting of —S(O)R″ and —SC(S)R 0 .

3. The method of claim 1 , wherein m=0.

4. The method of claim 1 , further comprising:

subjecting the polymer of a general formula (IV):

to a thermal conversion step at a temperature between 30° C. and 300° C., whereby a polymer is obtained comprising structural units of a formula (XXX):

5. The method of claim 4 , wherein the polymer of general formula (IV) comprises more than 25% of repeat units of a formula (XXX):

6. The method of claim 5 , wherein the polymer of general formula (IV) corresponds to a general formula (XXIII):

wherein:

Ar is substituted or unsubstituted, and is selected from the group consisting of triptycenylene, pentiptycenylene, and iptycenylene;

Ar′ is selected from the group consisting of arylene and heteroarylene, wherein Ar′ is unsubstituted or substituted with one or more substituents independently selected from the group consisting of C 1-20 alkyl, C 1-20 alkoxy, C 1-20 alkylsulfate, poly(ethylene oxide), oligo(ethylene oxide), aryl, and aryl-(C 1-4 alkyl), wherein said heteroarylene comprises up to 4 heteroatoms independently selected from the group consisting of oxygen, sulfur, and nitrogen;

R 3 , R 4 , R 10 and R 11 are independently selected from the group consisting of hydrogen, C 1-20 alkyl, cyclic C 3-20 alkyl, aryl, alkylaryl, arylalkyl, and heterocyclyl;

n is from 1 to 2000; and m is from 0 to 2000,

with the proviso that n/(n+m) is more than 0.25 and that when m is 0, Ar is not

wherein both asterisks indicate points of attachment of the Ar group in each Ar-containing monomeric moiety in the general formula (XXIII).

7. The method of claim 1 , further comprising:

applying on a substrate the polymer having a general formula (IV):

and subjecting said polymer to at least one of a heat treatment and an acid treatment, whereby said polymer is converted into a polymer comprising more than 25% of repeat units of general formula (XXX):

8. The method of claim 1 , wherein the polymer has a molecular weight above 10000 daltons.

9. The method of claim 1 , wherein the polymer has a polydispersity in a range of from 1 to 15.

10. The method of claim 1 , wherein the polymer has a polydispersity in a range of from 2 to 3.

11. The method of claim 1 , wherein the polymer has a formula:

wherein R is hydrogen.

12. The method of claim 1 , wherein the polymer has a formula:

wherein R is 2-ethylhexyloxy.