Extension of the chain‐end,free‐volume theory for predicting glass temperature as a function of conversion in hyperbranched polymers obtained through one‐pot approaches

Compared with linear polymers, more factors may affect the glass‐transition temperature (T_g) of a hyperbranched structure, for instance, the contents of end groups, the chemical properties of end groups, branching junctions, and the compactness of a hyperbranched structure. T_g's decrease with increasing content of end‐group free volumes, whereas they increase with increasing polarity of end groups, junction density, or compactness of a hyperbranched structure. However, end‐group free volumes are often a prevailing factor according to the literature. In this work, chain‐end, free‐volume theory was extended for predicting the relations of T_g to conversion (X) and molecular weight (M) in hyperbranched polymers obtained through one‐pot approaches of either polycondensation or self‐condensing vinyl polymerization. The theoretical relations of polymerization degrees to monomer conversions in developing processes of hyperbranched structures reported in the literature were applied in the extended model, and some interesting results were obtained. T_g's of hyperbranched polymers showed a nonlinear relation to reciprocal molecular weight, which differed from the linear relation observed in linear polymers. T_g values decreased with increasing molecular weight in the low‐molecular‐weight range; however, they increased with increasing molecular weight in the high‐molecular‐weight range. T_g values decreased with increasing log M and then turned to a constant value in the high‐molecular‐weight range. The plot of T_g versus 1/M or log M for hyperbranched polymers may exhibit intersecting straight‐line behaviors. The intersection or transition does not result from entanglements that account for such intersections in linear polymers but from a nonlinear feature in hyperbranched polymers according to chain‐end, free‐volume theory. However, the conclusions obtained in this work cannot be extended to dendrimers because after the third generation, the end‐group extents of a dendrimer decrease with molecular weight. Thus, it is very possible for a dendrimer that T_g increases with 1/M before the third generation; however, it decreases with 1/M after the third generation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1235–1242, 2004     

Conformation of nonideal hyperbranched polymer in ABn (n = 2, 4) type polymerization

The conformation of hyperbranched polymers from one pot polymerization with AB_n (n = 2, 4) type monomers, applying the reactive 3D bond fluctuation lattice model, are systematically studied using scaling relation R ～ N^λ, where R is the radius of gyration or the hydrodynamic radius of a hyperbranched polymer with the degree of polymerization N. The exponent λ was calculated at various monomer concentrations and group conversions. When the concentration of monomers with the equal reactivity of B groups increases from 0.1 to 0.9, the exponents λ_g and λ_h (corresponding to the radius of gyration and hydrodynamic radius, respectively) are in the ranges of 0.51–0.37 and 0.41–0.34 at the full conversion of A groups. Especially, we find that λ_g decreases linearly with the reaction conversion increasing. The ratio of z‐average radius, R_gz/R_hz, ranges from 1.08 to 1.32 and indicates that hyperbranched polymer is soft macromolecule with penetrable structure. In the case of AB₂ type monomer with unequal reactivities, λ displays complicated dependence on the reaction conversion and the reactivity ratio. The results of our simulation are consistent with those of experiments and theories, and valuable in better understanding the fundamental properties of hyperbranched polymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 610–616, 2010     

Acid chloride‐functionalized hyperbranched polyester for facile and quantitative chain‐end modification: One‐pot synthesis and structure characterization

Carboxylic acid chloride end‐functionalized all‐aromatic hyperbranched polyesters were prepared from the bulk polycondensation of the AB₂ monomer 5‐(trimethylsiloxy)isophthaloyl dichloride. The acid chloride end functionality of the hyperbranched polyester was modified in situ with methanol and yielded methyl ester ends in a one‐pot process. Chain‐end functionalization and esterification were quantitative according to both potentiometric titration and ¹H NMR analysis. The signals of ¹H and ¹³C NMR spectra of the esterified hyperbranched polyester were fully assigned from model compounds of the focal, linear, dendritic, and terminal units. The degree of branching and molecular weight averages measured by ¹H and ¹³C NMR spectroscopy and multidetector size exclusion chromatography increased systematically with increasing polymerization temperatures between 80 and 200 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2855–2867, 2002     

Blends of different linear polyamides with hyperbranched aromatic AB2 and A2 + B3 polyesters

To explore the possible applications of hyperbranched polymers for modifying linear polyamides, two hyperbranched aromatic polyesters characterized as high T_g polymers possessing phenolic end groups were used in melt mixing with partly aromatic polyamide and commercially available aliphatic polyamide‐6, respectively. Different amounts of both hyperbranched polyesters (from 1 wt % up to 20 wt %) were added to the polyamides, and the influence of these hyperbranched polyesters on the properties of the polyamides was investigated. The hyperbranched polyester based on an AB₂ approach was found to be the most effective modifier. A significant increase of the glass transition temperature of the final blend was detected. However, a remarkable reduction of crystallinity as well as complex melt viscosity of those blends was also observed. The use of an A₂+B₃ hyperbranched polyester as melt modifier for the polyamides was less effective for changing the thermal properties, and the complex melt viscosity of the final material increased since heterogeneous blends were formed. In contrast to that, generally, the addition of the AB₂ hyperbranched polyester to the polyamides resulted in homogeneous blends with improved T_g and processability. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3558–3572, 2009     

Synthesis and characterization of new soluble cardo polyesters derived from 1,1‐bis‐[4‐(4‐chlorocarboxyphenoxy)phenyl]‐4‐tert‐butylcyclohexane with various bisphenols by solution polycondensation

A new cardo diacid chloride, 1,1‐bis‐[4‐(4‐chlorocarboxyphenoxy)phenyl]‐4‐tert‐butylcyclohexane ( 4 ), was synthesized from 1,1‐bis‐[4‐(4‐carboxyphenoxy)phenyl]‐4‐tert‐butylcyclohexane in refluxing thionyl chloride. Subsequently, various new polyesters were prepared from 4 with various bisphenols by solution polycondensation in nitrobenzene using pyridine as a hydrogen chloride quencher at 150 °C. These polyesters were produced with inherent viscosities of 0.32–0.50 dL · g^?1. Most of these polyesters exhibited excellent solubility in a variety of solvents such as N,N‐dimethylformamide, tetrahydrofuran, tetrachloroethane, dimethyl sulfoxide, N,N‐dimethylacetamide, N‐methyl‐2‐pyrrolidinone, m‐cresol, o‐chlorophenol, and chloroform. These polymers showed glass‐transition temperatures (T_g's) between 144 and 197 °C. The polymer containing the adamantane group exhibited the highest T_g value. The 10% weight loss temperatures of the polyesters, measured by thermogravimetric analysis, were found to be in the range of 426–451 °C in nitrogen. These cardo polyesters exhibited higher T_g's and better solubility than bisphenol A‐based polyesters. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2951–2956, 2001     

Hyperbranched polymers as scaffolds for multifunctional reversible addition–fragmentation chain‐transfer agents: A route to polystyrene‐core‐polyesters and polystyrene‐block‐poly(butyl acrylate)‐core‐polyesters

Polydisperse hyperbranched polyesters were modified for use as novel multifunctional reversible addition–fragmentation chain‐transfer (RAFT) agents. The polyester‐core‐based RAFT agents were subsequently employed to synthesize star polymers of n‐butyl acrylate and styrene with low polydispersity (polydispersity index < 1.3) in a living free‐radical process. Although the polyester‐core‐based RAFT agent mediated polymerization of n‐butyl acrylate displayed a linear evolution of the number‐average molecular weight (M_n) up to high monomer conversions (>70%) and molecular weights [M_n > 140,000 g mol^?1, linear poly(methyl methacrylate) equivalents)], the corresponding styrene‐based system reached a maximum molecular weight at low conversions (≈30%, M_n = 45,500 g mol^?1, linear polystyrene equivalents). The resulting star polymers were subsequently used as platforms for the preparation of star block copolymers of styrene and n‐butyl acrylate with a polyester core with low polydispersities (polydispersity index < 1.25). The generated polystyrene‐based star polymers were successfully cast into highly regular honeycomb‐structured microarrays. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3847–3861, 2003     

Homologous series of alkylsilylphenyl‐substituted poly (p‐phenylenevinylene)s for light‐emitting diodes

Substituent‐induced electroluminescence polymers—poly[2‐(2‐dimethyldodecylsilylphenyl)‐1,4‐phenylenevinylene] [(o‐R₃Si)PhPPV], poly[2‐(3‐dimethyldodecylsilylphenyl)‐1,4‐phenylenevinylene] [(m‐R₃Si)PhPPV], and poly[2‐(4‐dimethyldodecylsilylphenyl)‐1,4‐phenylenevinylene] [(p‐R₃Si)PhPPV]—were synthesized according to the Gilch polymerization method. The band gap and spectroscopic data were tuned by the dimethyldodecylsilyl substituent being changed from the ortho position to the para position in the phenyl side group along the polymer backbone. The weight‐average molecular weights and polydispersities were 8.0–96 × 10⁴ and 3.0–3.4, respectively. The maximum photoluminescence wavelengths for (o‐R₃Si)PhPPV, (m‐R₃Si)PhPPV, and (p‐R₃Si)PhPPV appeared around 500–530 nm in the green emission region. Double‐layer light‐emitting diodes with an indium tin oxide/poly(3,4‐ethylenedioxythiophene)/polymer/Al configuration were fabricated with these polymers. The turn‐on voltages and the maximum brightness of (o‐R₃Si)PhPPV, (m‐R₃Si)PhPPV, and (p‐R₃Si)PhPPV were 6.5–8.7 V and 1986–5895 cd/m², respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2347–2355, 2004     

Triphenylantimony(V) o‐amidophenolates with unsymmetrical N‐aryl group for a reversible dioxygen binding

New triphenylantimony(V) o‐amidophenolates (AP‐Me,Et)SbPh₃ (1) and (AP‐Me,iPr)SbPh₃ (2) with unsymmetrically substituted N‐aryl groups and (AP‐Et,Et)SbPh₃ (3) with symmetrical N‐aryl group {AP‐R¹,R² is 4,6‐di‐tert‐butyl‐N‐[2‐alkyl(R¹),6‐alkyl(R²)‐phenyl]‐o‐amidophenolate dianion} were synthesized and characterized in detail. Complexes were examined for dioxygen activity. The unsymmetrical complexes 1 and 2 were found to form different geometrical isomers (A and B) of spiroendoperoxides [L‐R¹,R²(O₂)]SbPh₃ (4 and 5, respectively) with different dispositions of peroxide group and N‐aryl fragment (methyl and peroxide group are on the same side of the molecule in the less shielded isomer A, and on different sides in the more hindered isomer B). The isomer A prevails over isomer B, reflecting the possibility of steric control on the dioxygen‐binding reaction. Complex 3, where R¹ = R² = Et, formed the isomers 6A and 6B as 50:50. The ratio 4A:4B was 60:40 (for methyl‐ethyl containing complex 4) and it increased up to 80:20 for methyl‐isopropyl‐containing 5. The molecular structure of isomers 4A and 4B was confirmed by X‐ray analysis. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of hyperbranched polyimides with good organosolubility and thermal properties based on a new triamine and conventional dianhydrides

A triamine monomer, 1,3,5‐tris(4‐aminophenoxy)benzene (TAPOB), was synthesized from phloroglucinol and 4‐chloronitrobenzene, and it was successfully polymerized into soluble hyperbranched polyimides (HB PIs) with commercially available dianhydrides: 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA), and 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA). Different monomer addition methods and different monomer molar ratios resulted in HB PIs with amino or anhydride end groups. From ¹H NMR spectra, the degrees of branching of the amino‐terminated polymers were estimated to be 0.65, 0.62, and 0.67 for 6FDA–TAPOB, ODPA–TAPOB, and BTDA–TAPOB, respectively. All polymers showed good thermal properties with 10% weight‐loss temperatures (T₁₀'s) above 505 °C and glass‐transition temperatures (T_g's) of 208–282 °C for various dianhydrides. The anhydride‐terminated HB PIs showed lower T₁₀ and T_g values than their amino‐terminated counterparts. The chemical conversion of the terminal amino or anhydride groups of the 6FDA‐based polyimides into an aromatic imido structure improved their thermal stability, decreased their T_g, and improved their solubility. The HB PIs had moderate molecular weights with broad distributions. The 6FDA‐based HB PIs exhibited good solubility even in common low‐boiling‐point solvents such as chloroform, tetrahydrofuran, and acetone. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3804–3814, 2002     

Synthesis and properties of hyperbranched polyurethanes,hyperbranched polyurethane copolymers with and without ether and ester groups using blocked isocyanate monomers

Starting from 3,5‐diamino benzoic acid, 2‐hydroxy propyl[3,5‐bis{(benzoxycarbonyl)imino}]benzyl ether, an AB₂‐type blocked isocyanate monomer with flexible ether group, and 2‐hydroxy propyl[3,5‐bis{(benzoxycarbonyl)imino}]benzoate, an AB₂‐type blocked isocyanate monomer with ester group, were synthesized for the first time. Using the same starting compound, 3,5‐bis{(benzoxycarbonyl)imino}benzylalcohol, an AB₂‐type blocked isocyanate monomer, was synthesized through a highly efficient short‐cut route. Step‐growth polymerization of these monomers at individually optimized experimental conditions results in the formation of hyperbranched polyurethanes with and without ether and ester groups. Copolymerizations of these monomers with functionally similar AB monomers were also carried out. The molecular weights of the polymers were determined using GPC and the values (M_w) were found to vary from 1.5 × 10⁴ to 1.2 × 10⁶. While hyperbranched polyurethanes having no ether or ester group were found to be thermally stable up to 217 °C, hyperbranched poly(ether–urethane)s and poly(ester–urethane)s were found to be thermally stable up to 245 and 300 °C, respectively. Glass transition temperature (T_g) of polyurethane was reduced significantly when introducing ether groups into the polymer chain, whereas T_g was not observed even up to 250 °C in the case of poly(ester–urethane). Hyperbranched polyurethanes derived from all the three different AB₂ monomers were soluble in highly polar solvents and the copolymers showed improved solubility. Polyethylene glycol monomethyl ether of molecular weight 550 and decanol were used as end‐capping groups, which were seen to affect the thermal, solution, and solubility properties of polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3877–3893, 2007     

β‐Cyclodextrin polymer brushes based on hyperbranched polycarbosilane: Synthesis and characterization

In this article, our main goal is to combine hyperbranched polymer with β‐cyclodextrin (β‐CD) to establish a novel functional polymer species with core‐shell structure and supramolecular system for further application in inclusion technologies and the complex drugs delivery system. Therefore, two β‐CD polymer brushes based on hyperbranched polycarbosilane (HBP) as a hydrophobic core and poly(N,N‐dimethylaminoethyl methacrylate) (PDMA) carrying β‐CD units as a hydrophilic shell were synthesized. Hyperbranched polycarbosilane macroinitiator carrying ? Cl groups (HBP‐Cl) was also prepared by using 1,1,3,3‐tetrmethyldisiloxane, allyl alcohol, and chloroacetyl chloride as reagents. The molecular structures of HBP‐Cl macroinitiator and β‐CD polymer brushes were characterized by Fourier transform infrared spectroscopy (FTIR), ¹H nuclear magnetic resonance (¹H NMR), ¹³C nuclear magnetic resonance (¹³C NMR) spectroscopies, size exclusion chromatography/multi‐angle laser light scattering (SEC/MALLS) and laser particle size analyzer. The results indicate that the grafted chain length of two β‐CD polymer brushes can be controlled by changing the feed ratio. Differential scanning calorimetry (DSC) results show that two β‐CD polymer brushes have two glass transition temperatures (T_gs) from a hydrophobic core part and a hydrophilic shell part, respectively, and the T_g from PDMA is higher than that of HBP‐g‐PDMA. Thermalgravimetric analyzer (TGA) analysis indicates that the thermostability of two β‐CD polymer brushes is higher than that of HBP, but is lower than that of HBP‐g‐PDMA. Using phenolphthalein (PP) as a guest molecule, molecular inclusion behaviors for two β‐CD polymer brushes were studied. It reveals that two β‐CD polymer brushes possess molecular inclusion capability in PP buffer solution with a fixed concentration. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5036–5052, 2008     

Effects on Coordination of Thioether Sites. 4. Structural Analysis of η3-Tripodal Ligand Manganese(I) Complexes

Crystal structures of a series of manganese(I) complexes containing tripodal ligands were determined. For [η³-{CH₃C(CH₂PPh₂)₂(CH₂SPh)-P,P′,S}Mn(CO)₃]PF₆ ( 1 ): a = 10.856(3) Å, b = 19.698(3) Å, c = 17.596(5) Å, β = 96.17(2)°, monoclinic, Z = 4, P2₁/c, R(F_o) = 0.068, R_w(F_o) = 0.055 for 3617 reflections with I_o > 2σ(I_o). For [η³-{CH₃C(CH₂PPh₂)(CH₂SPh)₂-P,P′,S}Mn(CO)₃]PF₆ ( 2 ): a = 9.890(2) Å, b = 20.403(4) Å, c = 10.269(3) Å, β = 117.44(2)°, monoclinic, Z = 2, P2_l, R(F_o) = 0.050, R_w(F_o) = 0.037 for 1760 reflections with I_o > 2σ(I_o). For [η³-{CH₃C(CH₂PPh₂)₂(CH₂S)-P,P′,S}Mn(CO)₃] ( 4 ): a = 8.191(7) Å, b = 10.495(3) Å, c = 19.858(6) Å, α = 99.61(2)°, β = 96.17(2)°, γ = 92.70(4)°, triclinic, Z = 2, P-I, R(F_o) = 0.048, R_w(F_o) = 0.039 for 2973 reflections with I_o > 2σ(I_o). There is no significant difference in the bond lengths of Mn-S bonds among three species in their crystal structures [2.325(2) Å in 1; 2.358(4) in 2; 2.380(2) in 4], but the better donating ability of thiolate in complex 4 appears on the lower frequencies of its carbonyl stretching absorptions.     

Silver Vanadyl(IV) ortho‐Pyrophosphate: Synthesis,Crystal Structure,and Characterization of the (V≡O)2+ Group

Ag₆(V^IVO)₂(PO₄)₂(P₂O₇) was obtained by reaction of Ag₃PO₄ and (VO)₂P₂O₇ (sealed ampoule, 550 °C, 3 d). The crystal structure of the new mixed ortho‐pyrophosphate was determined from X‐ray single‐crystal data [Pnma, Z = 4, a = 12.759(3) Å, b = 17.340(4) Å, c = 6.418(1) Å, R₁ = 0.071, wR₂ = 0.184 for 3174 unique reflections with F_o > 4σ(F_o), 141 variables]. Ag⁺ ions are located in between layers [(V^IVO)₂(PO₄)₂(P₂O₇)]^6–. Equilibrium relations of the new phosphate to neighboring phases were determined. The electronic structure of the (V^IV≡O)²⁺ group was investigated by polarized electronic absorption spectroscopy (ν̃_1a = 9450 cm^–1, ν̃_1b = 9950 cm^–1, ν̃₂ = 14750 cm^–1), EPR spectroscopy [X‐ and Q‐band, powder and single crystal, orthorhombic crystal g‐tensor with g₁ = 1.9445(3), g₂ = 1.9521(3), g₃ = 1.9695(3)], and magnetic measurements (powder, μ_exp/μ_B = 1.71, Θ_p = –1.7 K).     

Synthesis and photoinitiating behavior of hyperbranched polymeric photoinitiators bearing coinitiator amine

A series of benzophenone (BP)‐terminated hyperbranched polyester (BoltornTM P1000), bearing amine moieties as synergists by reacting with piperidine, were synthesized as yellowish liquids with low viscosity, and used as polymeric photoinitiators (HPPIs). For comparison, acrylate groups were introduced to the terminals of hyperbranched polyester for obtaining a polymerizable photoinitiator. The chemical structures were characterized by FTIR and ¹H NMR spectroscopy. HPPIs and BP exhibited the similar absorptions by UV–vis spectroscopy. The photoinitiating behavior of HPPIs with trimethylolpropane triacrylate (TMPTA) as a trifunctional monomer was investigated by using photo‐DSC analysis. The results indicated that the maximum photopolymerization rate and unsaturation conversion of TMPTA initiated by HPPIs were both lower than that by BP. Among them, the HPPI with double tertiary amine moiety of BP moiety was found to be the most efficient photoinitiator. Additionally, the films cured with bisphenol A epoxy acrylate EB605 initiated by HPPIs were uniform and possessed high T_g from DMTA. Copyright © 2010 John Wiley & Sons, Ltd.     

Novel Polymer Clusters with a Uniform Chain Density

The thermal decomposition of polystyrene clusters prepared by using 4‐methacryloyloxy‐2,2,6,6‐tetramethylpiperidine‐N‐oxyl as a branching agent was studied. The weight‐average molar mass (M̄_w) and the radius of gyration (R_g) of the resultant clusters can be scaled as M̄_w ∝︁ R_g^{3.0 ± 0.1}, revealing that these clusters have a uniform chain density. Moreover, the dynamic properties of such clusters converge unexpectedly faster than the static properties as the molar mass decreases.     

Synthesis and properties of long‐chain branched poly(ether sulfone)s by self‐polycondensation of AB2 type macromonomers

Long‐chain branched poly(ether sulfone)s (PESs) were synthesized via self‐polycondensation of AB₂ macromonomers. The linear PES oligomers synthesized by self‐polycondensation of 4‐chloro‐4′‐(4‐hydroxyphenyloxy)diphenyl sulfone were terminated with 4‐(3,5‐methoxyphenoxy)‐4′‐fluorodiphenyl sulfone to form AB₂ macromonomer precursors. After conversion from methoxy to hydroxy groups, the AB₂ macromonomers were self‐polycondensed to form long‐chain branched PESs. NMR measurements support the formation of the target macromonomers ( = 2930–67,800 (g mol^?1); M_n = number average molecular weight) and long‐chain branched PESs. Gel permeation chromatography with multiangle light scattering measurements indicated the formation of high‐molecular‐weight (M_w) polymers over 10⁴. The root‐mean‐square radius of gyration (R_g) suggests that the shape of the long‐chain branched PES synthesized from small AB₂ macromonomers in solution is similar to that of hyperbranched polymers. Increasing resulted in larger R_g, suggesting a transition from hyperbranched to a linear‐like architecture in the resulting long‐chain branched PESs. Rheological measurements suggested the presence of strongly entangled chains in the long‐chain branched PES. Higher tensile modulus and smaller elongation at the break were observed in the tensile tests of the long‐chain branched PESs. It is assumed that the enhanced molecular entanglement points may act as physical crosslinks at room temperature. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1825–1831     

Light-scattering characterization of poly(ethylene terephthalate)

By using a closed-circuit filtration system, we have succeeded in clarifying poly(ethylene terephthalate) (PET) dissolved in hexafluoroisopropanol (HFIP). Such static properties as the radius of gyration R_g, the weight-average molecular weight M_w, and the second virial coefficient A₂ and such dynamic properties as the translational diffusion coefficient D, or its equivalent hydrodynamic radius R_h, and the second (diffusion) virial coefficient k_d were determined for several PET samples of different molecular weights by using light-scattering intensity and linewidth measurements. An empirical relation between D_o (or R_h) and M_w was established: R_h = (1.77±0.15)X10^?2 M with R_h and M_w expressed in units of nanometers and grams per mole, respectively. The empirical exponent α_D(ca. 0.58±0.01) is in good agreement with the less precisely determined intrinsic viscosity/molecular weight exponent α_η (ca. 0.71±0.02). Several intensity correlation functions were measured very precisely using long accumulation times. A Laplace inversion was performed using the singular-value decomposition technique. The approximate molecular weight distribution (MWD) determined by light-scattering spectroscopy was in reasonable agreement with a completely independent determination of MWD using gel permeation chromatography (GPC). It was interesting to note, though not surprising, that GPC showed emphasis on lower-molecular-weight fractions, while light-scattering emphasized higher-molecular-weight fractions. The agreement further strengthens some complementary aspects of the two techniques.     

Hydroxyl‐terminated hyperbranched aromatic poly(ether‐ester)s: Synthesis,characterization, end‐group modification,and optical properties

Novel AB₂‐type monomers such as 3,5‐bis(4‐methylolphenoxy)benzoic acid ( monomer 1 ), methyl 3,5‐bis(4‐methylolphenoxy) benzoate ( monomer 2 ), and 3,5‐bis(4‐methylolphenoxy)benzoyl chloride ( monomer 3 ) were synthesized. Solution polymerization and melt self‐polycondensation of these monomers yielded hydroxyl‐terminated hyperbranched aromatic poly(ether‐ester)s. The structure of these polymers was established using FTIR and ¹H NMR spectroscopy. The molecular weights (M_w) of the polymers were found to vary from 2.0 × 10³ to 1.49 × 10⁴ depending on the polymerization techniques and the experimental conditions used. Suitable model compounds that mimic exactly the dendritic, linear, and terminal units present in the hyperbranched polymer were synthesized for the calculation of degree of branching (DB) and the values ranged from 52 to 93%. The thermal stability of the polymers was evaluated by thermogravimetric analysis, which showed no virtual weight loss up to 200 °C. The inherent viscosities of the polymers in DMF ranged from 0.010 to 0.120 dL/g. End‐group modification of the hyperbranched polymer was carried out with phenyl isocyanate, 4‐(decyloxy)benzoic acid and methyl red dye. The end‐capping groups were found to change the thermal properties of the polymers such as T_g. The optical properties of hyperbranched polymer and the dye‐capped hyperbranched polymer were investigated using ultraviolet‐absorption and fluorescence spectroscopy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5414–5430, 2008     

Design,synthesis, photophysical,and electrochemical properties of DCM‐based conjugated polymers for light‐emitting devices

A series of conjugated hyperbranched polymers, hyperbranched copolymers, and linear polymers containing 2‐pyran‐4‐ylidenemalononitrile (acceptor) and triphenylamine/fluorene (donor) units were synthesized and characterized by FTIR, ¹H NMR, thermogravimetric analyses, differential scanning calorimetry, gel permeation chromatography, UV–visible, photoluminescence, and cyclic voltammetry measurements. All the polymers show red‐light emission in the range of 566–656 nm both in solution and in solid state. The quantum efficiency of the polymers was in the range of 56–82%. Among the six polymers synthesized, only polymers containing fluorene units show T_g and polymers based on triphenylamine not exhibit T_g. The band gap of these polymers were found to be reasonably low; hyperbranched copolymer containing fluorene unit shows lowest band gap of 2.18 eV due to the stabilization of LUMO energy level by the electron withdrawing ? CN groups. The thermal and solubility behavior of the polymers were found to be good. All the EL spectra of the devices (indium‐tin oxide/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)/polymer/2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline/tris(8‐hydroxyquinoline)aluminum)/LiF/Al) show red‐light emission, and the device fabricated with P3 and P4 shows maximum luminance and luminous efficiency of 4104 cd m^?2 and 0.55 cd Å^?1 and 3696 cd m^?2 and 0.47 cd Å^?1, respectively, indicates that they had the best carrier balance. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Molecular design,synthesis, and properties of Y‐type nonlinear optical polyester containing tricyanovinylthiophene with enhanced thermal stability of second harmonic generation

1‐{3,4‐Di‐(2‐hydroxyethoxy)phenyl}‐2‐(2‐thiophenyl)ethene (5) was prepared and condensed with terephthaloyl chloride to yield polyester (6). Polymer 6 was reacted with tetracyanoethylene to give a new Y‐type polyester (7) containing 1‐(3,4‐dioxyethoxy)phenyl‐2‐{5‐(2,2,3‐tricyanovinyl)‐2‐thiophenyl)}ethenyl groups as NLO‐chromophores, which are components of the polymer backbones. Polyester 7 is soluble in common organic solvents such as N,N‐dimethylformamide and acetone. Polymer 7 showed a thermal stability up to 300 °C in thermogravimetric analysis with glass transition temperature (T_g) obtained from differential scanning calorimetry near 126 °C. The second harmonic generation (SHG) coefficient (d₃₃) of poled polymer film at the 1560 nm fundamental wavelength was around 6.57 × 10^?9 esu. The dipole alignment exhibited high thermal stability up to the T_g, and there was no SHG decay below 125 °C due to the partial main‐chain character of polymer structure, which is acceptable for NLO device applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1911–1919, 2009