Soluble rigid–flexible polyethers containing bis(biphenyl)anthracene or bis(styryl)anthracene units in the main chain for light-emitting applications

New rigid–flexible polyethers containing bis(biphenyl)anthracene or bis(styryl)anthracene units in the main chain were synthesized and characterized by viscosimetry, thermal and mechanical analysis, NMR, UV-vis, and luminescence spectroscopy. The polyethers containing bis(styryl)anthracene units in the main chain form free-standing films either from solution casting or after melt pressing at temperatures where they are thermally stable. The length of the flexible spacer influences the thermal and mechanical behavior of these polymers. The isotropization temperature as well as the glass transition temperature show an odd–even effect depending on the spacer segment length. Films with high modulus at room temperature and glass transition temperatures in the range 74–103°C were obtained using dynamic mechanical analysis. These polymers show bright-yellow photoluminescence with maximum at 580 nm in solution. In the solid state, the luminescence maximum is either red or blue shifted depending on the number of the methylene units in the aliphatic segment. The polyethers containing bis(biphenyl)anthracene units in the main chain are blue-light-emitting polymers with photoluminescence maxima at 435 and 455 nm in solution. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3826–3837, 1999     

Adhesive liquid-crystalline polymers

The synthesis and characterization of liquid-crystalline polymers with possible good adhesive properties is reported. These polymers are prepared by alternating copolymerization of maleic anhydride and mesogenic alkenes. The spacer length m is varied (m = 2, 3, 4, 6, 8 and 9) and methoxybiphenyl is used as the mesogenic group. The glass transition temperature decreases and the isotropization temperature increases with spacer length. Depending on the spacer length and temperature, S_B and S_Ad mesophases can be observed. After annealing, spin-coated films of these polymers show very regular layered structures with a layer spacing similar to that in the bulk.     

New liquid crystalline di- and tetra-acrylates for network formation

New liquid crystalline diacrylates and tetra-acrylates containing four to six aromatic rings were synthesized and characterized, and their mesophase behaviour was investigated. They are designed to be used in combination with chiral molecules to form cholesteric mesophases which can be crosslinked by photopolymerization. The acrylates presented exhibit broad mesophase ranges since mesogenic moieties longer than three are employed. Most diacrylates show no isotropization, due to premature thermal polymerization above 180°C. Additionally, liquid crystalline dipropionates were synthesized as reference compounds which cannot be crosslinked, and selected examples of these exhibit isotropization temperatures as high as 238°C prior to thermal degradation. Substituents at the mesogenic moiety have a great influence on the mesophase characteristics. Bulky substituents such as the tert-butyl group, induce a nematic mesophase, whereas compounds with small substituents (e.g. OCH3) or unsubstituted molecules also exhibit smectic phases. Tetra-acrylates with unsubstituted and substituted mesogenic units feature nematic mesophases only as a result of the additional spacers attached. Here isotropization was observed without polymerization at temperatures around 120-160°C.     

Synthesis and mesomorphic behavior of a new series of side-chain liquid crystalline polymethacrylates bearing 2,6-naphthylene-based mesogen

A new homologous series of liquid crystalline (LC) polymethacrylates, the poly[ω-(2-phenoxycarbonyl-naphthalene-6-yloxy)alkyl methacrylate]s, in which the length of the alkyl spacer is varied between 3 and 12 methylene units, have been synthesized by free-radical polymerization. The prepared polymers were studied by IR and ¹H-NMR spectroscopy, viscosity measurements, differential scanning calorimetry (DSC), and polarized microscopy. Polymers with 3 or 4 methylene units spacer were glassy in nature, whereas those with 5–12 methylene units spacer exhibited smectic behavior. The glass transition temperatures decrease on increasing spacer length. The isotropization temperatures and the corresponding transition entropies showed an odd–even effect, with the odd members exhibiting the higher values. This effect attenuates on increasing spacer length. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2391–2399, 1999     

Thermotropic liquid‐crystalline poly(oxadiazole)s with poly(methylene) spacers: Preparation and extraordinary odd–even effect

A novel synthetic procedure for the preparation of poly(oxadiazole)s was developed with nucleophilic substitution of α,ω-alkanediols with oxadiazole-activated bisfluoride. Seven poly(oxadiazole)s were successfully prepared by the solution polymerization of 2,5-bis(4-fluorophenyl)-1,3,4-oxadiazole and various α,ω-alkanediols [HO (CH₂)_n OH, n = 5–10 or 12] in diphenyl sulfone at temperature greater than 230 °C with K₂CO₃ as a catalyst. The reduced viscosities of the poly(oxadiazole)s were 0.14–0.51 dL/g, and the decomposition temperatures were greater than 350 °C and decreased from 436 to 379 °C with increasing spacer length (n). Corresponding model compounds, consisting of two terminal mesogenic 2,5-bisphenyl-1,3,4-oxadiazole units and central poly(methylene) spacers, were also prepared for comparison. Both the polymers and model compounds exhibited an extraordinary odd–even effect: odd ones showed higher transition temperatures (melting and clearing temperatures). With differential scanning calorimetry, polarized optical microscopy (POM), and X-ray diffraction, we found that the nematic mesophase was the only texture in the melts except for the polymers with longer methylene units (n = 9), in which smectic mesophases were observed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 293–301, 2002     

Synthesis and thermal behaviours of side-chain liquid-crystalline poly[N-(4-methoxyazobenzene-4′-oxyalkyl)ethyleneimine]

A series of side-chain liquid-crystalline polymers, poly[N-(4-methoxyazobenzene- 4′-oxyalkyl)ethyleneimine](PEnZO), has been synthesised in which the number of methylene units in spacers varies from two to six. The structures of the synthesised monomers and polymers were confirmed by infrared (IR) and ¹H nuclear magnetic resonance (¹H NMR) spectroscopy. The thermal properties of these polymers have been investigated using differential scanning calorimetry (DSC), polarising optical macroscopic (POM) X-ray diffraction and thermogravimetric analysis (TGA). The test results indicated that the obtained polymers exhibited thermotropic liquid-crystalline mesomorphism of nematic type with schlieren textures. It was observed that the thermal behaviours of the polymers were strongly dependent on the degree of substitution and the length of spacers. Polymers containing less than 57% of mesogenic groups did not exhibit mesogenic phase and resembled amorphous polymer. A more pronounced odd–even effect in the melting points and their enthalpy changes was observed on increasing the spacer length in which the odd members displayed lower values, which were also slightly dependent on the substitution degree of polymers. The mesomorphic temperature ranges of odd members were wider than those of even members. The decomposition temperatures of copolymers were near 230°C.     

Synthesis and characterization of liquid crystalline polymethacrylates,polyacrylates, and polysiloxanes containing 4-methoxy-4′-hydroxy-α-methylstilbene-based mesogenic groups

The synthesis and characterization of polymethacrylates and polyacrylates containing 4-methoxy-4′-hydroxy-α-methylstilbene side groups attached either directly or through flexible spacers containing eleven, eight, six, three, and respectively two methylenic units, and of the polysiloxanes containing the same mesogenic group connected through flexible spacers containing eleven, eight, six, and respectively three methylenic units are described. All polymers exhibit thermotropic liquid crystallinity. The nature of the mesophase is determined by the spacer length. However, the nature of the polymer backbone determines the thermal stability of the mesophase. That is, for the same spacer length and similar polymer molecular weight, the most flexible polymer backbone leads to the highest isotropization temperature.     

Synthesis and characterization of side‐chain liquid‐crystalline poly(ethyleneimine)s with cyanobiphenyl groups

A series of polyethyleneimine‐based side‐chain liquid‐crystalline polymers substituted with different ratios of cyanobiphenyl as pendent mesogenic groups has been synthesized in which the spacer length varies between two and six methylene units. The structures of the synthesized polymers are confirmed by infrared and ¹H nuclear magnetic resonance spectroscopy. The thermal properties of these polymers have been investigated using differential scanning calorimetry, polarized optical microscopy and X‐ray diffraction. The results indicate that the thermal behaviour of the polymers is strongly dependent on the degree of substitution. Polymers containing more than 69% of mesogenic groups exhibit nematic‐type thermotropic liquid‐crystalline behaviour with schlieren textures. Below this limit, the polymers are amorphous. Polymers with a higher degree of substitution present the crystalline states. The phase transition temperatures increase and the mesomorphic temperature ranges widen with increasing degree of substitution. The clearing temperatures decrease as the spacer length increases. An odd–even effect in the clearing temperatures is observed and the odd members display the higher values.     

Side chain liquid crystalline diethanolamine‐based polyesters with methoxy and/or nitroazobenzene mesogenic moieties

Side‐chain polyesters based on diethanolamine and 5‐hydroxyisophthalic acid with mesogenic methoxyazobenzene and nitroazobenzene groups were synthesized and their liquid crystalline properties were examined.

Four different types of polyesters were prepared by using various combinations of monomers differing in the mesogen group and the length of the spacer. The thermal and structural properties depend on the type of polyester as well as on the side chain length. The glass transition and isotropization temperatures increase when the methoxyazobenzene group is bound to a diol and decrease when it is bound to an isophthalic acid. Most of the polyesters are thermotropic liquid crystals and form a nematic phase on heating. Some polyesters exhibit shear induced isotropisation to nematic transition up to 25°C above the isotropization temperature.     

Odd–even effect in biphenyl‐based symmetrical dimers with methylene spacer – evidence of the B4 phase

A series of 4‐decyloxy‐4′‐hydroxybiphenyl esters of α,ω‐alkanedicarboxylic acids containing two mesogenic units connected by a methylene spacer was synthesized. The mesogenic properties of the compounds were investigated by polarising optical microscopy, differential scanning calorimetry and X‐ray diffraction methods. A strong influence of the spacer length and its parity on the mesomorphic properties was found. A dramatic odd–even effect was observed for the clearing temperatures and entropies. Compounds with an even number of carbon atoms in the methylene spacer formed tilted smectic phases, whereas compounds with an odd number of carbon atoms in the spacer exhibited the B4 phase, characteristic of bent‐shaped molecules.     

New liquid crystalline di- and tetra-acrylates for network formation

New liquid crystalline diacrylates and tetra-acrylates containing four to six aromatic rings were synthesized and characterized, and their mesophase behaviour was investigated. They are designed to be used in combination with chiral molecules to form cholesteric mesophases which can be crosslinked by photopolymerization. The acrylates presented exhibit broad mesophase ranges since mesogenic moieties longer than three are employed. Most diacrylates show no isotropization, due to premature thermal polymerization above 180°C. Additionally, liquid crystalline dipropionates were synthesized as reference compounds which cannot be crosslinked, and selected examples of these exhibit isotropization temperatures as high as 238°C prior to thermal degradation. Substituents at the mesogenic moiety have a great influence on the mesophase characteristics. Bulky substituents such as the tert-butyl group, induce a nematic mesophase, whereas compounds with small substituents (e.g. OCH3) or unsubstituted molecules also exhibit smectic phases. Tetra-acrylates with unsubstituted and substituted mesogenic units feature nematic mesophases only as a result of the additional spacers attached. Here isotropization was observed without polymerization at temperatures around 120-160°C.     

Thermotropic polyesters. 1: Synthesis, characterization and thermal transition of poly[4,4-bis(ω-alkoxy)biphenyl isophthalate]

A new homologous series of thermotropic polyesters has been synthesized by polycondensation reaction between isophthaloyl chloride and mesogenic diols 4,4^′-bis(ω-hydroxyalkoxy)biphenyl in which the spacer length is varied from 3 to 6 methylene units. The thermal behavior of the polymers has been characterized using polarized light microscopy and differential scanning calorimetry (DSC). The odd members exhibit a smectic C (S_C) phase in a narrow temperature interval, while the even members form a smectic A (S_A) phase in a broader temperature range. All of the obtained compounds were characterized by conventional spectroscopic methods.     

Liquid crystal polymers 23. Steric and polar effects of large substituents in thermotropic aromatic polyesters with decamethylene spacers

A series of thermotropic aromatic polyesters based on a triad ester mesogenic unit containing an arylsulfonyl substituted hydroquinone group and a decamethylene spacer group was prepared. The large arylsulfonyl substituent was substituted in the para-position with either electron donating or accepting groups to study the effect of steric and polar interactions on the thermal transitions of these polymers and on the thermodynamic parameters of their isotropization transitions. All polymers formed nematic melts, and a regular decrease in T₁, ΔH₁ and ΔS₁ was observed with increasing molecular radius of the substituted hydroquinone group. However, a polarity or polarizability effect was superimposed on these relationships. Model compounds containing the same aromatic ester triad were prepared and their thermotropic properties were compared to those of the polymers. Essentially identical effects were observed for both.     

Synthesis and characterization of liquid crystalline copolymethacrylates,copolyacrylates, and copolysiloxanes containing 4-methoxy-4′-hydroxy-α-methylstilbene and 4-hydroxy-4′-methoxy-α-methylstilbene constitutional isomers as side-groups

The synthesis of methacrylates and acrylates containing 4-methoxy-4′-hydroxy-α-methylstilbene and 4-hydroxy-4′-methoxy-α-methylstilbene constitutional isomers attached to the polymerizable group through flexible spacers containing 11, 8, 6, 3, and respectively 2 methylenic units is described. The radical copolymerization of a 1/2 or 2/1 mole ratio of the two constitutional isomeric monomers led to thermotropic side-chain liquid crystalline polymers in all cases. The synthesis of copolysiloxanes based on the same constitutional isomeric mesogens as side groups, and flexible spacers containing 11, 8, 6, 5, and respectively 3 methylenic units is also described. All polymers were characterized by differential scanning calorimetry and optical polarization microscopy. The polymers containing 11 methylenic units in the spacer exhibit S_c mesomorphism, while the other polymers are nematic. Copolymethacrylates do not undergo side-chain crystallization. Only the copolyacrylate containing 11 methylenic units in the spacer exhibits side-chain crystallization. All the copolysiloxanes display side-chain crystallization. The number of melting transitions seen for these polymers decreases with increasing spacer length. Copolysiloxanes containing dissimilar spacer length were also prepared. Only the copolymer synthesized with highly dissimilar spacer lengths, i.e., containing 3 and 11 methylenic units, does not undergo side-chain crystallization. These results have demonstrated that while the type of mesophase is dictated only by the spacer length, the degree of decoupling of the motion of the side-groups from the motion of the main chain is strongly dependent on the nature of the polymer backbone. For the same mesogenic unit and spacer length, the thermal stability of the mesophase is also dictated by the nature of the polymer backbone. The use of constitutional isomers of mesogenic units as side groups in liquid crystalline polymers provides at least qualitative information on the degree of decoupling of the side groups from the polymer main chain.     

Liquid crystalline copolymers containing electron donor and acceptor mesogens with a chiral group in the spacer unit

Side-chain liquid crystalline polymers containing both mesogenic (carbazolylmethylene)aniline and (4′-nitrobenzylidene)aniline units with various spacer groups were prepared to examine effects of the structure of spacer groups on the liquid crystalline properties. The copolymer containing (R)-(+)-2-methylpropylene as a chiral group in the spacer unit induced a smectic phase; the copolymer with a trimethylene spacer of similar length to the chiral spacer exhibited a nematic phase. Smectic phases were observed for the copolymer containing the chiral spacer group when the proportion of the carbazolyl group was in the range of 0.55–0.88. For example, the copolymer with the proportion of the carbazolyl group of 0.68 expressed the smectic phase from 88° to 167°C. This isotropic temperature was 37° higher than the calculated value (130°C) based on an assumed copolymer composition without the electron donor–acceptor interaction. Thus, it is assumed that for the chiral copolymer containing both electron donor and acceptor groups, the thermal stability and the induction of the smectic phase were caused by both the electron donor–acceptor interaction and the existence of the chiral group in the spacer unit. © 1995 John Wiley & Sons, Inc.     

Mesogenic Unsymmetric dimers containing cholesteryl ester and tolane moieties

Among unsymmetric oligomesogens, chiral dimers formed by connecting a cholesteryl ester fragment with various aromatic mesogenic cores through a polymethylene spacer have been attracting much attention due to their remarkable thermal behaviour. In particular, dimers containing a diphenylacetylene segment having an alkoxy chain have shown interesting mesomorphic behaviour. In view of this a new series of unsymmetric dimers consisting of a diphenylacetylene moiety having an alkyl chain and a cholesteryl ester unit joined through a paraffinic spacer have been synthesized and their liquid crystalline properties characterized. The lengths of the central methylene spacer (C₃, C₄, C₅ and C₇) as well as that of the alkyl chain (n-butyl, n-pentyl, n-hexyl and n-heptyl) have been varied to establish structure–property relationships. These investigations have revealed that all the dimers exhibit smectic A, twist grain boundary and chiral neamtic (N*) phases with the exception of one of the dimers for which only the N* phase was observed. Some differences in the mesomorphic properties of the unsymmetric dimers containing odd or even parity methylene spacers have been observed. The majority of dimers having an even (C₄) parity paraffinic spacer show a blue phase while the dimers with odd (C₃, C₅ and C₇) parity spacers exhibit the chiral smectic (SmC*) phase. In some cases, the SmC* phase exists well below (?60°C) and above room temperature.     

Synthesis and characterization of side-chain liquid-crystalline poly(ethyleneimine)s with cyanobiphenyl groups

A series of polyethyleneimine-based side-chain liquid-crystalline polymers substituted with different ratios of cyanobiphenyl as pendent mesogenic groups has been synthesized in which the spacer length varies between two and six methylene units. The structures of the synthesized polymers are confirmed by infrared and ¹H nuclear magnetic resonance spectroscopy. The thermal properties of these polymers have been investigated using differential scanning calorimetry, polarized optical microscopy and X-ray diffraction. The results indicate that the thermal behaviour of the polymers is strongly dependent on the degree of substitution. Polymers containing more than 69% of mesogenic groups exhibit nematic-type thermotropic liquid-crystalline behaviour with schlieren textures. Below this limit, the polymers are amorphous. Polymers with a higher degree of substitution present the crystalline states. The phase transition temperatures increase and the mesomorphic temperature ranges widen with increasing degree of substitution. The clearing temperatures decrease as the spacer length increases. An odd-even effect in the clearing temperatures is observed and the odd members display the higher values.     

Effect of lateral substituents on the mesomorphic properties of side-chain liquid crystalline polysiloxanes containing 4-[(S)-2-methyl-1-butoxy]phenyl 4-(alkenyloxy)benzoate side groups

The synthesis of side-chain liquid crystalline polysiloxanes containing either 4-[(S)-2-methyl-1-butoxy]phenyl 4-(alkenyloxy)benzoate or laterally fluoro-, chloro-, bromo-, and methoxy-substituted 4-[(S)-2-methyl-1-butoxy]phenyl 4-(alkenyloxy)benzoate mesogenic side groups is presented. The mesomorphic properties of the synthesized polymers have been characterized by optical polarizing microscopy, differential scanning calorimetry, and X-ray diffraction measurements. The effects of spacer length and lateral substituent on the mesomorphic properties of the obtained polymers are examined. The five polymers which contain three methylene units in the spacers show no mesophase, while the five polymers which contain eleven methylene units in the spacer display smectic mesomorphism. Among the other fifteen polymers which contain respectively four, five, or six methylene units in the spacers, those with small fluoro and chloro substituents reveal respectively an S_A phase, while those with bulky bromo and methoxy substituents show no liquid crystalline behavior. The experimental results demonstrate that introducing a bulky lateral substituent into the mesogenic core of a polymer depresses the tendency to form a mesophase. Furthermore, the technique of thermally stimulated current has been used to study the dipolar relaxation mechanisms in a side-chain liquid crystalline polysiloxane. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2793–2800, 1997     

Synthesis and thermal properties of liquid-crystalline polyacrylates containing a carbazolyl group in the mesogen

The new acrylate monomers 4-(ω-acryloyloxyalkyloxy)-N-(9-methyl-2-carbazolylmethylene) anilines containing from 2 to 11 methylenic units in their alkyl group and a carbazolyl group in the mesogenic unit were synthesized and polymerized by azobisisobutyronitrile (AIBN) as radical initiator and by low-energy electron beam (EB) initiation. The thermal properties of the resulting polymers were examined using differential scanning calorimetry and thermal optical polarizing microscopy. The polymer prepared by AIBN with a hexamethylene spacer exhibited a nematic phase from 73 to 170°C and with an undecamethylene spacer exhibited a smectic phase from 55 to 202°C. The isotropization temperature of the polyacrylates increased with increasing the number of carbons of the methylenic spacer. The yield of the resulting polymer was changed by EB irradiation temperature from 4.5 to 41%. The highest yield was obtained when the monomer was polymerized in a liquid-crystalline phase. The same tendency was observed in the molecular weight of the resulting polymers. © 1994 John Wiley & Sons, Inc.     

Rigid-rod liquid crystalline polyesters based on n-alkoxyterephthalic acid and 4,4′-dihydroxybiphenyl

The synthesis and the characterization of a set of polymers obtained by polycondensation of n-alkoxyterephthalic acid (n = 1, 3, 5, 7) and 4,4′-dihydroxybiphenyl are reported. The n-alkoxy insertion promotes the processability of the material by lowering the melting temperature. All polymers show the nematic phase at about 300°C, almost independently of the length of lateral substituent. The isotropization is not observed up to 450°C, where thermal decomposition occurs. The temperature of glass transition decreases with increasing n, ranging from 170°C (n = 5) to 220°C (n = 1). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 263–267, 1998