Optimal extent of fluorination enabling strong temperature-dependent aggregation,favorable blend morphology and high-efficiency polymer solar cells

Temperature-dependent aggregation is a key property for some donor polymers to realize favorable bulk-heterojunction(BHJ)morphologies and high-efficiency(10%) polymer solar cells.Previous studies find that an important structural feature that enables such temperature-dependent aggregation property is the 2nd position branched alkyl chains sitting between two thiophene units.In this report,we demonstrate that an optimal extent of fluorination on the polymer backbone is a second essential structural feature that enables the strong temperature-dependent aggregation property.We compare the properties of three structurally similar polymers with 0,2 or 4 fluorine substitutions in each repeating unit through an in-depth morphological study.We show that the non-fluorinated polymer does not aggregate in solution(0.02 mg mL~(-1) in chlorobenzene) at room temperature,which results in poor polymer crystallinity and extremely large polymer domains.On the other hand,the polymer with four fluorine atoms in each repeating unit exhibits an excessively strong tendency to aggregate,which makes it difficult to process and causes a large domain.Only the polymer with two fluorine atoms in each repeating unit exhibits a suitable extent of temperature-dependent aggregation property.As a result,its blend film achieves a favorable morphology and high power conversion efficiency.This provides another key design rationale for developing donor polymers with suitable temperature-dependent aggregation properties and thus high performance.     

Differential scanning calorimetry and thermogravimetric analysis investigation of the thermal properties and degradation of some radiation‐grafted films and membranes

The influence of irradiation and grafting on the crystallinity of three base polymers has been investigated with differential scanning calorimetry. Grafting has the largest effect on the base polymer crystallinity and results in a reduction of the crystallinity. The thermal degradation of the base polymers and grafted films has been investigated with thermogravimetric analysis. The extent of the fluorination of the base polymer, the irradiation method, and the graft level all influence the thermal degradation and its activation energy. It is proposed that the variation of the chain lengths of the grafted polystyrene chains is actually a primary underlying factor responsible for the influence of these various parameters on the degradation process. The first results of a comparative thermal analysis of some fuel‐cell membranes are also presented, and the promise and shortcomings of this method are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2612–2624, 2004     

A calculation scheme for estimation of dielectric loss factors in polymers

For the quantitative estimation of dielectric loss tangent tanδ in linear and network polymers, the calculation scheme based on the Debye theory is proposed. The calculation is performed for both polar and nonpolar dielectrics in a wide frequency interval ranging from 10² to 10⁶ Hz. This calculation requires knowledge of only the chemical structure of a repeating unit in a linear polymer or a repeating fragment in a polymer network. Experiments on the estimation of frequency dependences of tanδ are conducted for polymer networks based on poly(urethanes) and poly(isocyanurates) of different compositions. A fair correlation between calculation and experimental data is obtained. It has been shown that tanδ tends to change with the increasing content of bulky isocyanurate network junctions that are responsible for the specific behavior of the system under the action of alternating mechanical and electric fields.     

Electrical Conduction Study of Polymers with Indophenine Repeating Units

It has been established that the dark conduction of isatin-[thiophene]-indophenine and of three polymers in which it is a repeating unit is described by the expression [sgrave] = [sgrave] exp (Eact/kT). The indophenine repeating units in the polymers are connected with a single bond, an oxygen atom, or a methylene group. The electronic spectra in solution and in the solid state indicate that these bonds between the basic units do not interrupt the conjugation along the chain. There is no correlation between the activation energy calculated from optical data and the thermal activation energy of conduction. The latter is considered as a sum of the energy necessary for the generation of the carriers and the energies needed to overcome the intramolecular and intermolecular potential barriers. The values of the parameters characteristic of the semiconducting properties are determined in the first place by the structure of the polymers as a solid body. Crystallinity tends to improve the electrophysical properties. The participation of heteroatoms and groups in the polymer chain, provided they do not interrupt the conjugation, has a favorable effect in cases where their presence improves the intermolecular interaction. A “compensation effect” is to be observed for all substances in vacuum and in air. The experimental data are best explained by the hopping model of electrical conduction.     

Synthesis of chiral polybinaphthyls with novel conjugated chromophores

An efficient strategy has been developed to incorporate new chromophores into chiral binaphthyl polymers. The repeating units of these polymers are made of conjugated structures with strongly electron-donating amino groups at the both ends. These optically active materials contain the highest possible density of chromophores in a polymer chain since every repeating unit in these polymers is a chromophore. They are soluble in common organic solvents and can be easily processed. The spectroscopic properties of these polymers are studied. The structural similarity of the chromophores in these chiral conjugated polymers with those of two-photon absorbing molecules may lead to interesting optical properties.     

Thermal degradation of a polyphenylquinoxaline in air and vacuum

A series of poly[2,2′-(1,4-phenylene)-6,6′-bis(3-phenylquinoxalines)] were prepared. These polymers had all the same repeating unit but differed in molecular weight and polymer chain endings. The thermal degradation characteristics in air and vacuum were determined by isothermal weight loss measurements. The temperature coefficients of thermal degradation (apparent activation energies) were also determined. Whereas the apparent activation energies for degradation in air showed a considerable dependency on the type of polymer chain endings, no such effect was observed upon pyrolysis in vacuo. A possible chain-end unzipping mechanism of degradation in air is postulated to explain these results.     

Synthesis and evaluation of a series of regular polyampholytes

A series of three true polyampholytes with unequivocally alternating acidic and basic groups attached directly to the skeletal backbone of the polymer chain have been prepared. This was accomplished by copolymerizing 3,6-diallyl-2-piperidone with the α,ω-dithiols containing 2-, 4-, and 6-methylene groups. The polymerization was carried out in an emulsion system initiated by 2,2′-azobisisobutyronitrile (AIBN), yielding soluble piperidone-containing polymers with molecular weights in the 20,000–30,000 range. The piperidone rings in the polymers were hydrolyzed by dilute sulfuric acid to yield the desired polyampholytes. Fibers were prepared by wet-spinning formic acid solutions of the polyampholyte into saturated salt solution or by melt-spinning. These fibers were quite elastic. We were unsuccessful in demonstrating that mechanical energy could be attained by the effect of pH on the fibers. Similarly, no pH effect could be elicited in Instron tests. The stress-relaxation curve showed a marked positive force–temperature effect characteristic of rubberlike materials with few crosslinks. In a check of transition temperatures, it was noted that on repeated runs the second-order transition temperature rose markedly, suggesting an irreversible change. Viscometric studies clearly demonstrated polyelectrolyte behavior. X-ray diffraction studies of the polyampholytes showed that maximum crystallinity and orientation occurred in the polymer containing as part of the repeating unit the 1,4-butane dithiol moiety.     

Use of microperlite in direct polymerization of lactic acid

PLA is one of the most frequently used biodegradable polymers. In this work, PLA was synthesized by direct condensation polymerization of lactic acid in the presence of microperlite to obtain enhanced thermal stability of PLA polymer. Molecular weights of the synthesized polymers were determined by GPC. Chemical structure analyses was done by FTIR. The degree of crystallinity was evaluated by DSC and XRD. Thermal stability of polymers was investigated by DSC and TGA. It has been observed that the existence of perlite has significantly increased the crystallinity and degradation temperature, therefore, enhanced the thermal stability of the PLA.     

Determination of glass-transition temperatures of polymers: A modified computational scheme

A modified computational scheme is developed for estimation of the glass-transition temperatures of linear and network polymers. Contributions of atoms and atomic groups involved in the main chain and side chains of a polymer are separated. The suggested scheme makes it possible to avoid multiple corrections immanent to earlier advanced glass-transition temperature calculation models. The calculated and experimental values of glass-transition temperatures for polymers of the most diverse classes are in a good agreement; R ² is 0.998. This scheme makes it possible to substantially simplify calculations, and it is applicable to polymers of all chemical structures with repeating units containing elements C, H, O, N, F, Cl, Si, and S.     

Fluorescent aromatic polyamides with urea binding sites and fluorene or dansyl signaling units

This work describes six novel fluorescent aromatic polyamides with bulky dansyl or fluorene pendant groups or with the fluorene moiety in the main chain. The fluorescent signaling dansyl or fluorene moieties are chemically connected to, or within, the main polymer chains through a urea group, a well-known binding site in supramolecular chemistry. These polyamides are amorphous and soluble in polar aprotic solvents and demonstrate a film-forming capability. They also show yellowish-green or blue fluorescence in solution and in the solid state depending on the signaling unit, with the former corresponding to the dansyl and the latter to the fluorene residue. The water uptake and the thermal behavior have also been evaluated and related to the chemical structure. The polar amide, urea, and sulfonamide groups give rise to a high water sorption of up to 3.8 water molecules per repeating unit. The thermal behavior has been investigated by means of DSC and TGA. The glass transition temperatures of the polymers are high (up to 331 °C) and the decomposition temperatures (around 300 °C) are due to the moderate thermal stability of the urea group.     

Thermoanalytical evaluation of readily available reference polymers

A commercial set of polymers has been characterized by TG-DTA, DSC, TMA, FTIR spectroscopy and X-ray diffraction analysis (XRD). Thermal and mechanical stability, as well as the polymer glass transition temperature,T _g, and melt temperature,T _m, have been documented. There is a good correlation between measuredT _g andT _m values and published data. The degree of polymer crystallinity for polyethylene has been verified by XRD. The credibility and stability of these reference polymers is based on a comparison of their thermal properties, over a wide range of temperatures from two versions of a reference set, published in 1979 (A) and 1994 (B). The thermal properties and crystallinity of these polymers have stood the test of time and are reliable, readily available and consistent.     

Polyindoloquinoxalines

Two polymers, containing 6H-indolo [2,3-b] quinoxaline as a repeating unit, have been prepared by polycyclization of 5,5′-biisatyl with 3,3′-diaminobenzidine, and of 5,5′-diisatyl ether with 3,3′,3,4′-tetraaminodiphenyl ether in polyphosphoric acid. Their structure was established by comparing the infrared and electronic spectra of the newly obtained polymers with the corresponding spectra of four model compounds synthesized for the purpose. The electronic spectra showed conjugation along the chain of both the polymer with ether bonds and the one with single bonds between the rings. The two polymers gave an electronic paramagnetic resonance signal. The polyindoloquinoxalines showed good thermal stability in air and in nitrogen, the better stability being manifested by the polymer with single bonds between the rings.     

Soluble LC polyesters and their blend behavior

Poly(p-phenylene terephthalate) with substituents on the hydroquinone or on both monomer units were synthesized with the aim to obtain soluble LC polyesters. Focus was given to phenylalkyl substitution. With one phenylalkyl group in the repeating unit the polyesters are crystalline with melting points > 300°C. With two substituents the crystallinity is very low or the polymers are amorphous. These polyesters are soluble in chloroform forming isotropic solutions. Isotropic films of polyesters obtained from these solutions either crystallize or become anisotropic if heated above the glass transition temperature. The exponent in the Kuhn-Mark-Houwink equation is 0.95. Some of the polyesters form homogenous ternary solutions with polycarbonate. Films of the blends show additivity of modulus with respect to both components.     

Alternative synthetic strategies for Schiff base derived liquid crystal polymers: A comparative study

Semiflexible liquid crystalline polymers based on Schiff bases as mesogenic cores have been synthesized through different synthetic strategies. The mesogenic cores are derived from 1,5-naphthalenediamine linked to a polymethylenic spacer by means of ether or ester groups. The synthetic strategies differ in the disconnection of the molecules to design the synthesis of the repeating units. Polymers were synthesized either as polyazomethines, where imine bonds are formed in the polymer synthesis, or as polyethers or polyesters, where the ether or ester groups are formed at the polymer-forming stage. The influence of the synthetic method and the linking groups between mesogenic core and flexible spacer on the thermal and mesogenic properties has been analyzed by DSC, thermogravimetry, and optical microscopy. The possibility of obtaining hydroxy-functionalized polymers by different synthetic strategies has been studied as well as the influence of these groups on the thermal and mesogenic properties. © 1996 John Wiley & Sons, Inc.     

Aromatic polyisophthalamides with iminobenzoyl pendant groups

Polyisophthalamides were prepared from aromatic diamines and 5-iminobenzoylisophthalic acid by the Yamazaki method of direct polyamidation catalyzed by triphenylphosphite. The properties of the polymers were measured and compared with the analogous unsubstituted polyisophthalamides. The incorporation of one iminobenzoyl pendant group per repeating unit gave rise to better solubility in strongly polar solvents. Higher content of amide groups per repeating unit allowed the modified polymers to absorb moisture to a greater extent than the parent polyisophthalamides. The glass transition temperatures were raised 20–30 by the presence of the pendant groups and they ranged from 290 to 317°. On the contrary, the substituted polymers showed lower initial decomposition temperatures, as measured by TGA, all of them beginning to decompose at about 410°. The mechanical properties of polymer films seemed not to be greatly affected by the pendant groups and only small differences were observed between substituted and unsubstituted polymers.     

Synthesis of soluble LC-polyesters

Soluble LC polymers were synthesized with the aim to approach molecular reinforcement. Chemical modification results in a decrease of the crystallinity and an increase of the solubility. Substitution of the amide hydrogen in poly(4-aminobenzoic acid) by a methyl group reduces the stiffness of the polymer very much, and as a result no lyotropic solutions are obtained. Poly(p-phenylene terephthalate) with substituents on the hydroquinone or on both monomer units were synthesized. With one phenylalkyl group in the repeating unit the polyesters are crystalline with melting points > 300°C. With two substituents the polymers form in many cases amorphous anisotropic glasses at room temperature. 2-Biphenyl is the most effective substituent with regard to increase of solubility. These polyesters form isotropic solutions in chloroform. Isotropic films obtained from these solutions become anisotropic on heating above the glass transition temperature. Films of polyester/polycarbonate blends show additivity of E-modulus with respect to both compounds.     

Poly(ethylene oxide)s hydrophobically modified. Adsorption and spreading at the air-water interface

A comparative study of spread and adsorbed monolayer of poly(ethylene oxide)s of different molecular weight hydrophobically modified with alkyl isocyanates of different length chain is reported. The modification of the polymer was carried out according to reported procedures. The polymers obtained were studied at the air-water interface by Langmuir isotherms for spread monolayers and by Gibbs isotherms for the adsorption process. Isotherms obtained are interpreted in terms of the hydrophobic and hydrophilic balance of the polymers. Limiting area per repeating unit (A(0)) and collapse pressure (pi(c)) from spread monolayers were obtained. Spread monolayers of the hydrophobically modified polymers show larger collapse pressure values than unmodified polymer monolayers. In the adsorption process the excess surface concentration Gamma(infinity), area per repeat unit sigma, and efficiency of the adsorption were determined. The values of the area occupied per repeat unit in adsorbed monolayer (sigma) were larger than those of the spread monolayer. The efficiency of the adsorption of poly(ethylene oxide)s increases with the hydrophobic modification and with the alkyl chain length.     

Structure of a self-assembled hydrogen-bonded ‘living’ main chain liquid crystalline polymer

A main chain hydrogen-bonded liquid crystalline polymer was formed by melt mixing two complementary components, A and B, which in their individual states do not exhibit liquid crystallinity. The structure of the polymer and the thermal stability of its mesophase were studied using synchrotron radiation SAXS/WAXS/DSC at Daresbury (UK) and by variable temperature Fourier transform infrared. The chain extension, or “polymerization” process, was accelerated at the point when the polymer formed a liquid crystalline phase upon cooling from the isotropic melt. The polymer has an aabb chain structure and forms a smectic layer with a length of the A-B repeating unit. The hydrogen-bonded main chain polymer studied here is a monotropic liquid crystal. Above 150°C, it exhibits kinetic stabilization of its monotropic smectic phase. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1617–1624, 1998     

SYNTHESIS AND PROPERTIES OF NEW MESOGEN-JACKETED LIQUID CRYSTALLINE POLYMERS*

Some new mesogen-jacketed liquid crystalline polymers (MJLCP) with polymer backbones, spacers, andmesogenic units of different structures were synthesized by radical polymerization. The mesomorphic behavior of thesepolymers was examined using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Theirliquid crystallinity is influenced by the variation of polymer backbone, spacer, mesogenic unit and its terminal groups. Theresults show that 1) a more flexible polymer main-chain is more favorable to the formation of a liquid crystal phase, while 2)a flexible spacer will decrease the "Jacket Effect" and the liquid crystallinity and 3) a subtle modification of the terminalgroups on the mesogenic unit may also have a significant influence on properties of the polymers.     

Effect of chirality on pi-stacking in styrene and maleimide alternating copolymers

The effect of different chiral sequences in alternating copolymers of styrene and maleimide, poly(styrene-alt-dimethyl-N,N-propylamide) (SMI) was studied. The methods used for the SMI also applied to the general class of alternating copolymers of styrene and various maleimides. Only racemo-diisotactic polymers can associate into complexes because of the symmetrically distributed phenyl groups and maleimide monomers. This polymer is isotactic with respect to the chiral site of the styrene monomers (R, S) and isotactic with respect to the chirality of the maleimide [racemo (RR, SS)]. The maleimide, racemo (SS or RR) chirality, and the complementary S or R chirality in the styrene moiety form the repeating unit of racemo-diisotactic SMI. Structural deviations from the isotactic configurations induces an asymmetry in the distribution of styrene monomers and introduce bends in the polymer backbone, which prevent association through pi-stacking interactions. Semiempirical PM3 calculations on the SMI polymer have shown that this pi-stacking occurs when the polymers are separated by a distance about 10 A, and each pi-stacking pair formed from the styrene monomers has a stabilization energy of about 12 kJ/mol.