The present invention relates to polythiophenes, particularly regioregular head-to-tail poly(3-alkylthiophenes) (HT-PATs), block copolymers made therefrom, and their methods of formation. The present invention provides HT-PATs with well-defined, specific end-groups, functionalization of the defined HT-PATs, and incorporation of end group functionalized HT-PATs into block copolymers with structural polymers. The intrinsically conductive diblock and triblock copolymers, formed from the HT-PATs, have excellent conductivity and low polydispersities that are useful in a number of applications. The block copolymers of the present invention have been found to exhibit conductivities that range from a low of 10−8 S/cm for certain applications to as high as several hundred S/cm or more.
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1. An intrinsically conductive copolymer, the copolymer having a conductivity ranging from 10−8 S/cm to 300 S/cm, wherein the copolymer is a polyurethane copolymer.
2. An intrinsically conductive copolymer, the copolymer, having a conductivity ranging from 10−8 S/cm to 300 S/cm, wherein the copolymer includes a structural polymer comprising an atrp(atom-transfer-radical-polymerization)-polymerizable segment.
3. An intrinsically conductive copolymer, the copolymer having a conductivity ranging from 10−8 S/cm to 300 S/cm, wherein the copolymer has at least one intrinsically conducting polymer segment, the copolymer including a structural polymer comprising an atrp(atom-transfer-radical-polymerization)-polymerizable segment.
47. An intrinsically conductive polythiophene copolymer, the copolymer having a conductivity ranging from 10−8 S/cm to 300 S/cm, wherein the copolymer is formed from the polymer having the structure:
##STR00031##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1.
55. An intrinsically conductive copolymer, the copolymer having a conductivity ranging from 10−8 S/cm to 300 S/cm, wherein the copolymer is formed from a poly-(3-substituted) thiophene diol having the structure:
##STR00032##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1.
39. An intrinsically conductive polythiophene copolymer, the copolymer having a conductivity ranging from 10−8 S/cm to 300 S/cm, wherein the copolymer is formed from the polymer having the structure:
##STR00030##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1,
the polymer being formed from a polymerization reaction in major amounts of at least 90% by weight.
15. An intrinsically conductive polythiophene copolymer, the copolymer having a conductivity ranging from 10−8 S/cm to 300 S/cm, wherein the copolymer is formed from the polymer having the structure:
##STR00026##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, X is a halogen, and n is greater than 1,
the polymer being formed from a polymerization reaction in major amounts of at least 90% about 75% by weight.
31. An intrinsically conductive polythiophene copolymer, the copolymer having a conductivity ranging from 10−8 S/cm to 300 S/cm, wherein the copolymer is formed from the polymer having the structure:
##STR00029##
wherein R is selected from the group consisting of alkyl, polyether, and aryl; n is greater than 1; A is selected from the group consisting of alkyl and aromatic, and FG is a functional group selected from the group consisting of primary alkyl amine and primary alcohol.
23. An intrinsically conductive polythiophene copolymer, the copolymer having a conductivity ranging from 10−8 S/cm to 300 S/cm, wherein the copolymer is formed from the protected thiophene polymer having the structure:
##STR00027##
wherein PFG is a protected hydroxyl or amine functional group, and A is selected from the group consisting of alkyl and aromatic, the protected thiophene polymer formed from a polythiophene polymer, the polymer having the structure:
##STR00028##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, X is a halogen, and n is greater than 1, the polymer being formed from a polymerization reaction in major amounts of at least 90% about 75% by weight.
4. The copolymer of
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This application is a divisional of U.S. application Ser. No. 10/004,782, filed Dec. 4, 2001, issued as U.S. Pat. No. 6,602,974, which is incorporated by reference in its entirety, and is related to copending U.S. application Ser. No. 10/417,244, filed Apr. 16, 2003.
, and typically in amounts of at least about 95% by weight
in which R represents the resistance and W is the width of a solid film. The measurement results are listed in Table 2.
This example illustrates the preparation and properties of HT-PHT-block-polymethylacrylate (PMA) diblock copolymers.
The synthesis is the same as that described in Example 4 except that methyl acrylate monomer was used in the ATRP step. NMR and size exclusion chromatography also were used to characterize these diblock copolymers. The characterization results are listed in Table 3.
TABLE 3
Characterization Data of the Compositions, Molecular Weights,
Molecular Weight Distributions and Electrical Conductivity of
HT-PHT-Block-PMA Diblock Copolymers
Mn
Mn
Mw/
Conductivity
Sample
n
M
(1HNMR)
(SEC)
Mn
(S/cm)
(PHTn-b-PMAm)
42
25
9,300
16,100
1.15
116
1
(PHTn-b-PMAm)
42
42
10,800
17,800
1.15
49
2
(PHTn-b-PMAm)
42
117
17,300
23,900
1.19
7.1
3
Both AFM and TEM have confirmed the presence of “nano-wire” networks in the solid films of the diblock copolymers casted from their solution in toluene or xylene. FIG. 5 and
The conductivity measurement of these diblock copolymers was performed in the same way as described in Example 3. The results are also listed in Table 3.
This example illustrates the preparation and properties of PS-block-HT-PHT-block-PS and PMA-block-HT-PHT-block-PMA triblock copolymers.
The preparation was carried out as illustrated in Scheme 4. A difunctional ATRP macroinitiator was synthesized. HT-PHT diol was dissolved in anhydrous THF under nitrogen. To this solution triethylamine and 2-bromopropionyl bromide were added. After the reaction was carried out at room temperature for about 12 hours, the polymer was precipitated in methanol. The polymer was purified through dissolving in THF and precipitation again in methanol. After drying in vacuum, the polymer was used as difunctional initiator to perform the ATRP polymerization of styrene and methyl acrylate. The ATRP procedure was the same as that described in Example 4.
The characterization results of these triblock copolymers are listed in Table 4.
TABLE 4
Characterization Data of the Compositions, Molecular Weights,
Molecular Weight Distributions and Electrical Conductivity of
Triblock Copolymers Containing Regioregular Head-to-Tail
Polyhexylthiophene (PHT).
Mn
Mn
Mw/
Conductivity
Sample
n
M
(1HNMR)
(SEC)
Mn
(S/cm)
(PSm/2-b-PHTn-b-
56
86
18,500
25,500
1.21
5.2
PSm/2) 1
(PSm/2-b-PHTb-b-
56
251
35,600
38,100
1.25
0.43
PSm/2) 2
(PSm/2-b-PHTn-b-
56
822
94,900
93,600
1.51
0.05
PSm/2) 3
(PMAm/2-b-PHTn-
56
122
20,100
29,700
1.29
3.3
b-PMAm/2) 1
(PMAm/2-b-PHTn-
59
352
46,100
50,400
1.41
1.6
b-PMAm/2) 2
(PMAm/2-b-PHTn-
56
625
74,500
72,300
1.66
0.076
b-PMAm/2) 3
This example illustrates the preparation and properties of polyurethane containing HT-PHT.
Chemical incorporation of HT-PHT into polyurethane was performed as shown in Scheme 5. A two-shot process was used to carry out the synthesis. The stoichiometric amounts of HT-PHT diol prepared as described in Example 3 was dissolved in anhydrous THF in a flask equipped with a mechanical stirrer, reflux condenser and a dropping funnel. A few drops of dibutyltin dilaurate were added as catalyst. At reflux temperature, tolyl diisocyanate (TDI) was added dropwise with constant stirring and the reaction was continued for 2 hours to ensure endcapping of the polyhexylthiophene-diol by the TDI. The required quantity of 1,4-butanediol and PEG in THF was then added over a period of half an hour. The reaction was continued for 3 hours and the excess THF was distilled off. The viscous polymer solution was then cast and cured at room temperature in dry atmosphere.
Three polyurethane samples with different percentages of HT-PHT were synthesized. The weight percentage of HT-PHT in these three samples are 10%, 6.4%, and 0.6% respectively. After doped with iodine, the four-point probe method was employed to measure the conductivities of these polyurethane films. The results are listed in Table 5.
TABLE 5
Conductivities of Polyurethane Samples Containing HT-PHT
wt % of HT-PHT
10%
6.40%
0.60%
Conductivity (s/cm)
0.13
0.48
4.6 × 10−5
The following example is a procedure comparison for the polymerization of regioregular HT-PAT using ZnCl2 (set forth in Example 1) versus MgBr2.
An anhydrous diisopropylamine (1.4 ml, 10 mmol) and anhydrous THF (50 ml) were placed in a 100 ml flask. This mixture was cooled to a temperature of −76° C., and 4 ml of 2.5M Butyllithium was added. The solution was warmed to 0° C., stirred at that temperature for 5 minutes and cooled back to a temperature of −76° C. To this reaction mixture containing LDA was added 2-bromo-3-hexylthiophene (2.47 g, 10 mmol) and the solution was stirred at −50° C. for 1 hour. This was followed by addition of anhydrous MgBr2.Et2O (2.6 g, 10 mmol) at −60° C. and the reaction was stirred at that temperature for 1 hour. The reaction was then slowly allowed to warm up to 0° C., whereupon all MgBr2.Et2O had reacted. To the above mixture 35 mg of Ni(dppp)Cl2 was added and the mixture was stirred at room temperature for 1 hour. The polymer was then precipitated with methanol. After filtration, the polymer was purified by Soxhlet extraction with methanol, hexane, CH2Cl2 and finally THF. 0.32 g of polymer was obtained from the THF fraction after removing the THF (yield is 37%). MALDI analysis, H/Br: about 75%, H/H: about 20%, Br/Br: about 5%.
The regioregular polymers, and the methods of forming the same provide the diblock and triblock copolymers having excellent conductivity and low polydispersities that are useful in a number of commercially important applications. Examples include light emitting diodes (LEDs), polymer sensors, biosensors, field-effect transistors, flat panel displays, televisions, roll up displays, smart cards, phone cards, chemical sensory materials, and nonlinear optical materials. Moreover, phase separation of block copolymers can produce micro- or nanoscale sheets, cylinder or spheres that could be used to fabricate micro- or nanoscale electronic and optical devices, such as nanoscale transistors.
Although the foregoing description has necessarily presented a limited number of embodiments of the invention, those of ordinary skill in the relevant art will appreciate that various changes in the components, details, materials, and process parameters of the examples that have been herein described and illustrated in order to explain the nature of the invention may be made by those skilled in the art, and all such modifications will remain within the principle and scope of the invention as expressed herein in the appended claims. It will also be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications that are within the principle and scope of the invention, as defined by the appended claims.
Liu, Jinsong, Sheina, Elena E., McCullough, Richard D., Ewbank, Paul C.
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