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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24. A method of forming a polymer, comprising:
combining a soluble thiophene monomer with an amide base and zinc chloride at a temperature ranging from −78° C. to −60° C.; and
adding an effective amount of a ni(II) catalyst to initiate a polymerization reaction.
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.
85. A method of forming a polyurethane copolymer, comprising,
providing a poly-(3-substituted) thiophene diol having the structure:
##STR00041##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1;
adding at least one dihydroxyl functional compound and at least one polyisocyanate to the diol to form the polyurethane copolymer.
10. A method of forming a polymer, comprising:
combining a soluble thiophene monomer with an amide base and a divalent metal halide; and
adding an effective amount of a ni(II) catalyst to initiate a polymerization reaction to form at least 90% about 75% by weight of the polymer having the structure
##STR00027##
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.
80. A method of forming a triblock copolymer, comprising,
providing a poly-(3-substituted) thiophene diol having the structure:
##STR00039##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1,
adding an atrp (atom-transfer-radical-polymerization) initiator and a base to the diol to form a atrp macroinitiator; and
adding CuBr, at least one atrp ligand, and at least one radically polymerizable monomer to the atrp macroinitiator to form the triblock copolymer.
57. A method of forming a poly-(3-substituted) thiophene diol, comprising:
combining a soluble thiophene with an organomagnesium reagent, wherein the organomagnesium reagent has the formula R′MgX′ and R′ is a substituent selected from the group consisting of alkyl, vinyl and phenyl and X′ is a halogen, to form at least 90% by weight of a polythiophene intermediate polymer having the structure:
##STR00036##
wherein R is a subsistent selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1;
introducing aldehyde groups to both ends of a chain of the intermediate polymer; and
reducing the aldehyde groups to yield the poly-(3-substituted) thiophene diol.
72. A method of forming a diblock copolymer, comprising:
providing a deprotected polymer having one functional end group having the structure:
##STR00037##
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;
adding an atrp (atom-transfer-radical-polymerization) initiator and a base to the deprotected polymer to form an atrp macroinitiator; and
adding CuBr, at least one atrp ligand, and at least one radially polymerizable monomer to the atrp macroinitiator to form the diblock copolymer.
46. A method of forming a polymer, comprising:
combining a soluble thiophene monomer with an amide base and zinc chloride at a temperature ranging from −78° C. to −60° C.;
adding an effective amount of a first ni(II) catalyst to initiate a polymerization reaction and form an intermediate polymer;
adding a derivative compound represented by the formula PFG-A-MX′ and a second ni(II) catalyst to the intermediate polymer to form a protected thiophene polymer, wherein PFG is a protected hydroxyl or amine functional group, A is selected from the group consisting of alkyl and aromatic, M is a selected from the group consisting of Zn and Mg, and X′ is a halogen; and
deprotecting the protected thiophene polymer in an acid environment to form the deprotected polymer having one functional end group.
84. A method of forming a polyurethane copolymer, comprising
combining a soluble thiophene with an organomagnesium reagent, wherein said organomagnesium reagent has the formula R′MgX′ and R′ is a substitute selected from the group consisting of alkyl, vinyl and phenyl and X′ is a halogen, to form at least 90% by weight of a polythiophene intermediate polymer having the structure:
##STR00040##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1;
introducing aldehyde groups to both ends of a chain of the, intermediate polymer;
reducing the aldehyde groups to yield a poly-(3-substituted) thiophene diol;
adding at least one dihydroxyl functional compound and at least one polyisocyanate to the diol to form the polyurethane copolymer.
76. A method of forming a triblock copolymer, comprising
combining a soluble thiophene with an organomagnesium reagent, wherein said organomagnesium reagent has the formula R′MgX′ and R′ is a substituent selected from the group consisting of alkyl, vinyl and phenyl and X′ is a halogen, to form at least 90% by weight of a polythiophene intermediate polymer having the structure:
##STR00038##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1;
introducing aldehyde groups of both ends of a chain of the intermediate polymer;
reducing the aldehyde groups to yield a poly-(3-substituted) thiophene diol;
adding an atrp (atom-transfer-radical-polymerization) initiator and a base to the diol to form a atrp macroinitiator; and
adding CuBr, at least one atrp ligand, and at least one radically polymerizable monomer to the atrp macroinitiator to form the triblock copolymer.
38. A method of forming a polymer, comprising:
combining a soluble thiophenemonomer with an amide base and a divalent metal halide;
adding an effective amount of a first ni(II) catalyst to initiate a polymerization reaction to form at least 90% about 75% by weight of an intermediate polymer having the structure:
##STR00029##
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;
adding a derivative compound represented by the formula PFG-A-MX′ and a second ni(II) catalyst to the intermediate polymer to form a protected thiophene polymer, wherein PFG is a protected hydroxyl or amine functional group, A is selected from the group consisting of alkyl and aromatic, M is a selected from the group consisting to Zn and Mg, and X′ is a halogen; and
deprotecting the protected thiophene polymer in an acid environment to form the deprotected polymer having one functional end group.
68. A method of forming a diblock copolymer, comprising:
combining a soluble thiophene monomer with an amide base and zinc chloride at a temperature ranging from −78° C. to −60° C.;
adding an effective amount of a first ni(II) catalyst to initiate a polymerization reaction and form an intermediate polymer;
adding a derivative compound represented by the formula PFG-A-MX′ and a second ni(II) catalyst to the intermediate polymer to form a protected thiophene polymer, wherein PFG is a protected hydroxyl or amine functional group, A is selected from the group consisting of alkyl and aromatic, M is a selected from the group consisting of Zn or Mg, and X is a halogen; and
deprotecting the protected thiophene polymer in an acid environment to form a deprotected polymer having one functional end group;
adding an atrp initiator and a base to the deprotected polymer to form a atrp macroinitiator; and
adding CuBr, at least one atrp ligand, and at least one radically polymerizable monomer to the atrp macroinitiator to form the diblock copolymer.
3. The polythiophene polymer of
4. The polythiophene polymer of
5. The polythiophene polymer of
6. The polythiophene polymer of
7. The polythiophene polymer of
0. 9. The polythiophene polymer of
11. The method of
12. The method of
14. The method of
19. The method of
20. The method of
21. The method of
0. 23. The method of
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.
26. The method of
31. The method of
32. The method of
33. The method of
0. 34. The method of
35. The method of
36. The method of
39. The method of
40. The method of
42. The method of
43. The method of
44. The method of
45. The method of
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.
48. The method of
49. The method of
50. The method of
51. The method of
52. The method of
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 the polymer of
54. The protected thiophene polymer of
wherein R is selected from the group consisting of alkyl, polyester, 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,
the deprotected polymer formed from the polymer of
56. The deprotection polymer of
58. The method of
61. The method of
0. 63. The method of
0. 64. The method of
65. The method of
66. The method of
67. The method of
71. The method of
75. The method of
79. The method of
83. The method of
86. An electrically conductive or optically sensitive polymeric material formed from the method of
87. An electrically conductive or optically sensitive polymeric material formed from the method of
88. An electrically conductive or optically sensitive polymeric material formed from the method of
89. An electrically conductive or optically sensitive polymeric material formed from the method of
90. An electrically conductive or optically sensitive polymeric material formed from the method of claim 89 84.
91. An electrically conductive or optically sensitive polymeric material formed from the method of
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This invention was made with government support under NSF Grant CHE-0107178. The United States government may have rights in this invention.
1. Technical Field
The present invention is directed, generally, to polythiophenes, and, more particularly, to head-to-tail coupled regioregular polythiophenes, block copolymers made therefrom, and methods of forming the same.
2. Background
Conducting polymers, such as polythiophenes (PTs), represent a class of polymers that are lightweight, highly processable and exhibit relatively high environmental stability, thermal stability, and electrical conductivity. These materials can be synthetically tailored to achieve desired properties such as melting point, electrical conductivity, optical and microwave absorbance and reflectance, and electroluminescene. Compared to inorganic metals and semiconductors, electrically conductive polymers have been found to be promising candidates for numerous applications, ranging from electronic and optical devices, such as field-effect transistors, sensors, light-emitting diodes (LEDs), rechargeable batteries, smart cards, and non-liner optical materials, to medical applications, such as artificial muscles.
Due, in part, to the increased demand for employing conducting polymers into a wide range of electrical and optical equipment, efforts have been made to advance the ways in which electrically conducting polymers can be improved for even greater integration into these applications. Numerous attempts to produce electrically conductive polymers that exhibit the electronic and optical properties of semiconductors and metals and the mechanical and processing advantages of typical plastics have, thus far, yielded little success. These attempts typically employ one of two distinct methods—the formation of polymer blends, and the synthesis of block copolymers.
Techniques that incorporate blends and/or composites of conducting polymers and conventional polymers include chemical and electrochemical in situ polymerization. These methods include mechanically mixing two or more conducting and conventional polymers to form a polymer blend. Blending methods are relatively simple and cost effective when compared to methods that produce block copolymers, and can be found in various publications, such as, for example, H. L. Wang, L. Toppare, J. E. Fernandez, Macromolecules, 23, 1053 (1990); K. Koga, S. Yamasaki, K. Narimatsu, M. Takayanagi, Polym. J . 1989, 21(1989), 733 (1989); Synthetic Metals, 21, 41 (1989); Synthetic Metals, 28, c435 (1989); Synthetic Metals, 37, 145 (1990); Synthetic Metals, 37, 195 (1990); Macromolecules, 25, 3284 (1992); Synthetic Metals, 22, 53 (1987); Macromolecules, 22, 1964 (1989); Polymer, 39, 1992 (1989): and U.S. Pat. Nos. 5,427,855 and 5,391,622.
Although the methods disclosed in these publications are said to provide some advancement in the area of electrically conductive polymers, these methods include various processing difficulties. For example, one significant difficultly relates to the tendency of the blends to form highly heterogeneous two-phase systems. The high degree of phase separation is a result of the relatively small enthalpy of mixing typically associated with macromolecular systems that limits the level of molecular intermixing needed to alter the physical properties of each of the components of the blends. Accordingly, conducting polymer blends that exhibit both high electrical conductivity and good mechanical properties are very limited. In addition, conventional blending methods typically encounter the existence of a sharp threshold, known as “percolation” threshold, which is the lowest concentration of conducting particles needed to form continuous conducting chains when incorporated into another material. The percolation threshold for conductivity of the blends is met at about 16% volume fraction of the conducting polymer. This threshold is described in detail in Synthetic Metals, 22(1), 79, (1987) and the references cited therein. Due, in part, to the “percolation” effect, it is difficult to tailor the moderate electrical conductivity for a variety of uses that include the dissipation of static charge.
The second approach to improve the processability and mechanical properties of electrically conductive polymers is through the synthesis of block copolymers. Block copolymers are typically formed from the reaction of conducting polymers and conventional polymers (i.e. structual polymers such as polystyrenes, polyacrylates, polyurethanes, and the like), the product of which exhibit a combination of the properties of their segment polymers. Accordingly, segment polymers can be chosen to form copolymer products having attractive mechanical properties. Furthermore, the covalent linkage between the polymer segments allows phase separation to be limited at the molecular level, thereby providing a more homogeneous product relative to polymer blends.
Although the advantages of block copolymers over polymer blends have long been recognized, it has been found that incorporating the conducting polymer segments into block copolymers is difficult. Intrinsic electrically conducting polymers consist of a backbone of repeating units with π conjugation that limits their formation by conventional polymerization methods, such as radical polymerization, ionic polymerization or ring opening polymerization. Therefore, methods to incorporate electrically conducting polymers with other polymers are limited, and typically include linkage of short conjugated segments by flexible spacers to multi-block polymers. These previously reported block copolymers have not shown good electrical properties or nanophase separation morphology due to the short π conjugation. Recently, there have been a number of attempts to synthesize block copolymers that exhibit a nanophase separation morphology. Synthetic Metals, 41-43, 955 (1991); Nature, 369, 387 (1994); Synthetic Metals, 69, 463 (1995); Science, 279, 1903 (1998); Macromolecules, 29, 7396 (1996); Macromolecules, 32, 3034 (1999); J. Am. Chem. Soc., 122, 6855 (2001); J. Am. Chem. Soc., 120, 2798 (1998). However, few of the synthesized block copolymers have been found to exhibit good electrical properties, such as conductivity. Moreover, the processes employed to synthesize these polymers include tedious step-by-step organic synthesis to build the block copolymers, or they lack diversity in the types of copolymers available.
The discovery of additional applications and new technologies for conductive block copolymers is subject, in large part, to molecular designers ability to control the structure, properties, and function of their chemical synthesis. Those in the art have come to recognize that structure plays an important, if not critical role, in determining the physical properties of conducting polymers. PTs represent a class of conducting polymers that are thought to have the potential for furthering the advancement of new and improved applications for conductive block copolymers.
Because of its asymmetrical structure, the polymerization of 3-substituted thiophenes produces a mixture of PT structures containing three possible regiochemical linkages between repeat units. The three orientations available when two thiophene rings are joined are the 2,2′, 2,5′, and 5,5′ couplings. When application as a conducting polymer is desired, the 2,2′ (or head-to-head) coupling and the 5,5′ (or tail-to-tail) coupling, referred to as regiorandom couplings, are considered to be defects in the polymer structure because they cause a sterically driven twist of thiophene rings that disrupt conjugation, produce an amorphous structure, and prevent ideal solid state packing, thus diminishing electronic and photonic properties. The steric crowding of the solubilizing groups in the 3 position leads to loss of planarity and less π overlap. In contrast, the 2,5′ (or head-to-tail (HT) coupled) regioregular PTs can access a low energy planar conformation, leading to highly conjugated polymers that provide flat, stacking macromolecular structures that can self-assemble, providing efficient interchain and intrachain conductivity pathways. The electronic and photonic properties of the regioregular materials are maximized.
HT-poly-alkylthiophenes (HT-PATs) are conjugated polymers in which the alkylthiophene rings are connected in the head-to-tail fashion. One of the inventors of the present invention developed the first regioselective synthesis of this class of polymer (R. D. McCullough et al., J. Am. Chem. Soc., 113, 4910 (1993), and references cited therein) and a method to synthesize these polymers on a large scale (U.S. Pat. No. 6,166,172), which are incorporated by reference herein in their entirety. The “defect-free” conjugation in these polymer chains leads to better π-π between-chain overlap and give rise to highly ordered, conducting polymer structures in solid state films. This solid state structural order allows charges to travel freely without being trapped or retarded by defects. Therefore, regioregular HT-PAT films have much higher conductivity than their regiorandom analogs. In fact, HT-PATs represent one of the classes of polymers with the highest electrical conductivity.
Although the McCullough methods have made important strides in the formation of electrically conductive block copolymers, certain deficiencies exist in their application and the resultant products formed therefrom. Most significantly, it has been difficult, if not impossible, to predict with any degree of certainty the type and amount of specific end groups, such as H/Br, H/H, and Br/Br, that are produced through application of these methods. Because the end group formation of HT-PAT product is random, the reaction typically forms products mainly having amounts of either the H/H or H/Br end groups that range from 35% to 65% by weight, but are typically nearly evenly divided in amounts ranging from 45% to 55% by weight. As a result, these methods do not provide HT-PATs with well-defined, specific end-groups, inhibiting functionalization of the defined HT-PATs and incorporation of end group functionalized HT-PATs into block-copolymers with structural polymers, such as polystyrenes, polyacrylates, polyurethanes, and the like.
Accordingly, the need exists for HT-PATs and electrically conducting block copolymers formed therefrom that exhibit, or can be synthesized to exhibit, characteristics of the electronic and optical properties of semiconductors and metals and mechanical properties and processing advantages of typical plastics, and their methods of manufacture. Furthermore, new methods for preparing HT-PATs and block copolymers formed therefrom are needed that are efficient, economical, provide end group control, and produce novel block copolymers containing HT-PAT conductive segments that have both high electrical conductivity and excellent mechanical properties.
This invention provides HT-PATs and their methods of formation, as well as block copolymers and their methods of formation from the HT-PATs, having attractive mechanical properties and excellent electrical conductivity. Specifically, this invention provides syntheses of block copolymers containing regioregular head-to-tail poly(3-alkylthiophenes) conductive segments.
In one embodiment, a polythiophene polymer is provided having the structure:
##STR00001##
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 polythiophene polymer is formed from a polymerization reaction in major amounts of at least 90% by weight.
In another embodiment, a polythiophene polymer is provided having the structure:
##STR00002##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1. The polythiophene polymer is formed from a polymerization reaction in major amounts of at least 90% by weight.
The present invention provides a method of forming the polymers set forth above. One method includes combining a soluble thiophene monomer with an amide base and a divalent metal halide, and adding an effective amount of a Ni(II) catalyst to initiate a polymerization reaction to form at least 90% by weight of the polymer having the structure:
##STR00003##
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.
Another method of forming a polymer is set forth herein, and includes combining a soluble thiophene monomer with an amide base and zinc chloride at a temperature ranging from −78° C. to −60° C., and adding an effective amount of a Ni(II) catalyst to initiate a polymerization reaction.
In another embodiment, the present invention provides a method of forming a polymer that includes combining a soluble thiophene with an organomagnesium reagent. The organomagnesium reagent has the formula R′MgX′. R′ is a substituent selected from the group consisting of alkyl, vinyl and phenyl and X′ is a halogen, to form at least 90% by weight of a polythiophene polymer having the structure:
##STR00004##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1.
The present invention also provides a method of forming a polymer that includes combining a soluble thiophene monomer with an amide base and a divalent metal halide, and adding an effective amount of a first Ni(II) catalyst to initiate a polymerization reaction to form at least 90% by weight of an intermediate polymer having the structure:
##STR00005##
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. Added to the intermediate polymer is a derivative compound represented by the formula PFG-A-MX′ and a second Ni(II) catalyst to form a protected thiophene polymer, wherein PFG is a hydroxyl or amine functional group, A is selected from the group consisting of alkyl and aromatic, M is a selected from the group consisting of Zn or Mg, and X′ is a halogen. The thiophene polymer is deprotected in an acid environment to form the deprotected polymer having one functional end group.
In another embodiment, the present invention provides a method of forming a polymer that includes combining a soluble thiophene monomer with an amide base and zinc chloride at a temperature ranging from −78° C. to −60° C. and adding an effective amount of a first Ni(II) catalyst to initiate a polymerization reaction and form an intermediate polymer. A derivative compound represented by the formula PFG-A-MX′ and a second Ni(II) catalyst is added to the intermediate polymer to form a protected thiophene polymer, wherein PFG is a hydroxyl or amine functional group, A is selected from the group consisting of alkyl and aromatic, M is a selected from the group consisting of Zn or Mg, and X′ is a halogen. The protected thiophene polymer is deprotected in an acid environment to form the deprotected polymer having one functional end group.
In another aspect of the present invention, a protected thiophene polymer is provided having the structure:
##STR00006##
wherein PFG is a protected hydroxyl or amine functional group, and A is selected from the group consisting of alkyl and aromatic.
The present invention also provides a deprotected polymer having one functional end group having the structure:
##STR00007##
where 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.
In addition, another aspect of the present invention is a method of forming a poly-(3-substituted) thiophene diol, comprising combining a soluble thiophene with an organomagnesium reagent, wherein the organomagnesium reagent has the formula R′MgX′ and R′ is a substituent selected from the group consisting of alkyl, vinyl and phenyl and X′ is a halogen, to form at least 90% by weight of a polythiophene intermediate polymer having the structure:
##STR00008##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1. Aldehyde groups are introduced to both ends of a chain of the intermediate polymer, and reduced to yield the poly-(3-substituted) thiophene diol.
The present invention also provides a thiophene polymer having aldehyde end groups, the polymer having the structure:
##STR00009##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, and is greater than 1.
In yet another embodiment, the present invention provides a poly-(3-substituted) thiophene diol having the structure:
##STR00010##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1.
The present invention also provides a method of forming a diblock copolymer that includes combining a soluble thiophene monomer with an amide base and zinc chloride at a temperature ranging from −78° C. to −60° C. and adding an effective amount of a first Ni(II) catalyst to initiate a polymerization reaction and form an intermediate polymer. A derivative compound represented by the formula PFG-A-MX′ and a second Ni(II) catalyst is added to the intermediate polymer to form a protected thiophene polymer, wherein PFG is a hydroxyl or amine functional group, A is selected from the group consisting of alkyl and aromatic, M is a selected from the group consisting of Zn or Mg, and X is a halogen. The protected thiophene polymer is deprotected in an acid environment to form a deprotected polymer having one functional end group. An ATRP initiator and a base are added to the deprotected polymer to form an ATRP macroinitiator. CuBr, at least one ATRP ligand, and at least one radially polymerizable monomer are added to the ATRP macroinitiator to form the diblock copolymer.
Another method of forming a diblock copolymer is presented herein, and includes providing a deprotected polymer having one functional end group having the structure:
##STR00011##
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. An ATRP initiator and a base are added to the deprotected polymer to form a ATRP macroinitiator. CuBr, at least one ATRP ligand, and at least one radically polymerizable monomer are added to the ATRP macroinitiator to form the diblock copolymer.
In another embodiment, the present invention provides a method of forming a triblock copolymer, and includes combining a soluble thiophene with an organomagnesium reagent, wherein the organomagnesium reagent has the formula R′MgX′ and R′ is a substituent selected from the group consisting of alkyl, vinyl and phenyl and X′ is a halogen, to form at least 90% by weight of a polythiophene intermediate polymer having the structure:
##STR00012##
wherein R is a substituted selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1. Aldehyde groups are introduced to both ends of a chain of the intermediate polymer, and reduced to yield a poly-(3-substituted) thiophene diol. An ATRP initiator and a base are added to the diol to form an ATRP macroinitiator. CuBr, at least one ATRP ligand, and at least one radially polymerizable monomer are added to the ATRP macroinitiator to form the triblock copolymer.
In another embodiment, the present invention provides a method of forming a triblock copolymer that includes providing a poly-(3-substituted) diol having the structure:
##STR00013##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1. An ATRP initiator and a base are added to the diol to form an ATRP macroinitiator. CuBr, at least one ATRP ligand, and at least one radially polymerizable monomer are added to the ATRP macroinitiator to form the triblock copolymer.
In yet another aspect of the present invention, a method of forming a polyurethane copolymer is provided that includes combining a soluble thiophene with an organomagnesium reagent, wherein the organomagnesium reagent has the formula R′MgX′ and R′ is a substituent selected from the group consisting of alkyl, vinyl and phenyl and X′ is a halogen, to form at least 90% by weight of a polythiophene intermediate polymer having the structure:
##STR00014##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1. Aldehyde groups are introduced to both ends of a chain of the intermediate polymer, and reduced to yield a poly-(3-substituted) thiophene diol. At least one dihydroxyl functional compound and at least one polyisocyanate are added to the diol to form the polyurethane copolymer.
In another embodiment of the present invention, a method of forming a polyurethane copolymer is provided that includes providing a poly-(3-substituted) thiophene diol having the structure:
##STR00015##
wherein R is a substituent selected from the group consisting of alkyl, polyether, and aryl, and n is greater than 1. At least one dihydroxyl functional compound and at least one polyisocyanate are added to the diol to form the polyurethane copolymer.
The present invention also provides intrinsically conductive copolymers, such as diblock, triblock, and polyurethane copolymers, having a conductivity ranging from 10−8 S/cm to 150 S/cm or more.
The present invention also provides an electrically conductive or optically sensitive polymeric material formed from any of the methods or comprising the polymers set forth herein.
The foregoing summary, as well as the following detailed description of the preferred embodiments, will be better understood when read in conjunction with the appended drawings. In the drawings:
It is to be understood that certain descriptions of the present invention have been simplified to illustrate only those elements and limitations that are relevant to a clear understanding of the present invention, while eliminating, for purposes of clarity, other elements. Those of ordinary skill in the art, upon considering the present description of the invention, will recognize that other elements and/or limitations may be desirable in order to implement the present invention. However, because such other elements and/or limitations may be readily ascertained by one of ordinary skill upon considering the present description of the invention, and are not necessary for a complete understanding of the present invention, a discussion of such elements and limitations is not provided herein. For example, as discussed herein, the materials of the present invention may be incorporated, for example, in electronic and optical devices that are understood by those of ordinary skill in the art, and, accordingly, are not described in hi detailed herein.
Furthermore, compositions of the present invention may be generally described and embodied in forms and applied to end uses that are not specifically and expressly described herein. For example, one skilled in the art will appreciate that the present invention may be incorporated into electrical and optical devices other than those specifically identified herein.
Other than in the operating examples, or unless otherwise expressly specified, all of the numerical ranges, amounts, values and percentages such as those for amounts of materials, times and temperatures of reaction, ratios of amounts, and others in the following portion of the specification may be read as if prefaced by the word “about” even though the term “about” may not expressly appear with the value, amount, or range. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Furthermore, when numerical ranges of varying scope are set forth herein, it is contemplated that any combination of these values inclusive of the recited values may be used.
As used herein, the term “blend” refers to a combination of at least one conducting polymer component with at least one other non-conductive polymer component, wherein the molecular intermixing of the polymer components is insufficient to significantly alter the physical properties of the individual components of the blend. As used herein, the term “copolymer” refers to a reaction product of at least two polymer components whereby the physical properties of each of the components is significantly altered, and the covalent linkage between the polymer segments allows phase separation to be limited at the molecular level to form a more homogeneous product relative to a polymer blend. The phrase “intrinsically conductive”, as used herein, refers to an electrically conductive block copolymer having at least one conducting segment, such as polythiophene, pyrrole, p-phenylenevinylene, and the like, attached thereto.
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 such as polystyrenes, polyacrylates, polyurethanes, and the like. The HT-PATs, the diblock and triblock copolymers formed therefrom, and the methods of forming the same provide block copolymers having excellent conductivity and low polydispersities that are useful in a number of applications.
The HT-PATs of the present invention and their methods of formation are set forth below in Part A. The block copolymers formed from the HT-PATs and their methods of formation are set forth below in Part B.
The end group functionalization of HT-PATs of the present invention is shown in Schemes 1 and 2. Scheme 1 illustrates the synthesis of a well-defined regioregular HT-PATs with one functional end group, and proceeds as follows: ##STR00016##
Thiophene compound 1 may be various purified halogenated thiophene monomers having the attached R group defined above. Any suitable thiophene monomer may be employed depending on the product that is desired. For example, one suitable thiophene monomer staring material is 2-bromo-3-hexylthiophene. Compound 1 should be relatively pure to give the highest molecular weight yields. Typically, purity levels are at least 95%, and may be about 99% or more pure. Purified compound 1 may be formed by methods known by those of ordinary skill in the art.
As set forth below in the examples, compound 1 may be reacted with about one equivalent of an amide base, such as lithium diisopropylamide (LDA), followed by transmetallation with at least about one equivalent of zinc chloride. The reaction proceeds at cryogenic temperatures of −60° C. or less (i.e. colder), and typically range from −78° C. to −60° C. It has been found that zinc chloride, When reacted with the thiophene starting materials at cryogenic temperatures, provides particularly good results when compared to other divalent metal halides, such as magnesium bromide. Comparative examples are illustrated below in Examples 1 and 8.
A Ni(II) catalyst, such as, for example, 1,3-diphenylphosphinopropane nickel(II) chloride (Ni(dppp) Cl2) or 1,2-bis(diphenylphosphino)ethane nickel(II) chloride (Ni(dppe)Cl2), may be added to the reaction in amounts ranging from 0.5 to 10 mol %. The Ni(II) catalyst may be added either at the cryogenic reaction temperature at which the LDA and zinc chloride is added, and then warmed to room temperature (about 25° C.), or the catalyst may be added during the warming period or after the solution is warmed to room temperature. The solution may be quenched with an excess of suitable solvent, such as methyl alcohol, at room temperature to form intermediate PAT polymer 2.
As illustrated in Scheme 1, polymer 2 is a regioregular HT-PAT, and has major amounts of H/Br end groups. The synthesis allows the H/Br end groups present in the HT-PAT product to be controlled and accurately calculated. As set froth below, the H/Br end groups are present as product in at least 90% 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 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
Conduc-
Mn
Mn
Mw/
tivity
Sample
n
m
(1HNMR)
(SEC)
Mn
(S/cm)
(PHTn-b-PMAm) 1
42
25
9,300
16,100
1.15
116
(PHTn-b-PMAm) 2
42
42
10,800
17,800
1.15
49
(PHTn-b-PMAm) 3
42
117
17,300
23,900
1.19
7.1
Both AFM and TEM have confirmed the present 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 were performed in the same way as described in Example 3. The result 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 difuctional 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-PSm/2) 1
56
86
18,500
25,500
1.21
5.2
(PSm/2-b-PHTn-b-PSm/2) 2
56
251
35,600
38,100
1.25
0.43
(PSm/2-b-PHTn-b-PSm/2) 3
56
822
94,900
93,600
1.51
0.05
(PMAm/2-b-PHTn-b-PMAm/2) 1
56
122
20,100
29,700
1.29
3.3
(PMAm/2-b-PHTn-b-PMAm/2) 2
59
352
46,100
50,400
1.41
1.6
(PMAm/2-b-PHTn-b-PMAm/2) 3
56
625
74,500
72,300
1.66
0.076
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 stirred, 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
0.048
4.6 × 10−6
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-3hexylthiophene (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 has 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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