Biodegradable comb-dendritic tri-block copolymers consisting of poly(ethylene glycol) and poly(l-lactide): Synthesis, characterizations, and regulation of surface morphology and cell responses

A series of well-defined dumbbell-shaped tri-block copolymers consisting of comb-like poly(l-lactide) (PLLA) and linear poly(ethylene glycol) (PEG) with narrow molecular weight distributions and varied PLLA arm lengths have been synthesized via the sequential preparation of terminal dendronized polyhydric PEG and ring-opening polymerization (ROP) of l-lactide (LA). The terminal dendronized polyhydric PEG was prepared by the conjugation of amine-terminated fourth-generation polyester dendrons with NHS-activated PEG followed by the deprotection of acetonide groups. The length of PLLA arms can be readily controlled by the feed molar ratio of LA monomer to the hydroxyl groups in PEG macro-initiator. Differential scanning calorimetric (DSC) measurements and thermal gravimetric analysis (TGA) have been performed to indicate that the glass transition temperature (T_g), melting point (T_m), degree of crystallinity (χ_c), and onset decomposition temperature (T_d) of the copolymers are lower than those of the linear polylactide (LPLLA). Self-organized porous structures have been found in the copolymer films after solution casting and solvent evaporation. Honeycomb-like surface morphology could be achieved by adjusting the length of PLLA arms. Meanwhile, surface chemistry of the copolymer films such as surface hydrophobicity and the capability of adsorbing protein increase with the length of PLLA arms. Controllable material properties have been correlated with the in vitro cell responses. No cytotoxicity of the dumbbell-shaped copolymers has been found using rabbit bone marrow stromal cells (BMSCs). Human embryonic kidney (HEK) 293T cells have been used to reveal the effect of surface characteristics on cell attachment and proliferation. It has been found that cell proliferation has been enhanced significantly on the surfaces of the copolymers with longer PLLA arm lengths because of more favorable surface physicochemical properties.     

Induced helical backbone conformations of self-organizable dendronized polymers

Control of function through the primary structure of a molecule presents a significant challenge with valuable rewards for nanoscience. Dendritic building blocks encoded with information that defines their three-dimensional shape (e.g., flat-tapered or conical) and how they associate with each other are referred to as self-assembling dendrons. Self-organizable dendronized polymers possess a flat-tapered or conical self-assembling dendritic side chain on each repeat unit of a linear polymer backbone. When appended to a covalent polymer, the self-assembling dendrons direct a folding process (i.e., intramolecular self-assembly). Alternatively, intermolecular self-assembly of dendrons mediated by noncovalent interactions between apex groups can generate a supramolecular polymer backbone. Self-organization, as we refer to it, is the spontaneous formation of periodic and quasiperiodic arrays from supramolecular elements. Covalent and supramolecular polymers jacketed with self-assembling dendrons self-organize. The arrays are most often comprised of cylindrical or spherical objects. The shape of the object is determined by the primary structure of the dendronized polymer: the structure of the self-assembling dendron and the length of the polymer backbone. It is therefore possible to predictably generate building blocks for single-molecule nanotechnologies or arrays of supramolecules for bottom-up self-assembly. We exploit the self-organization of polymers jacketed with self-assembling dendrons to elucidate how primary structure determines the adopted conformation and fold (i.e., secondary and tertiary structure), how the supramolecules associate (i.e., quaternary structure), and their resulting functions. A combination of experimental techniques is employed to interrogate the primary, secondary, tertiary, and quaternary structure of the self-organizable dendronized polymers. We refer to the process by which we interpolate between the various levels of structural information to rationalize function as retrostructural analysis. Retrostructural analysis validates our hypothesis that the self-assembling dendrons induce a helical backbone conformation in cylindrical self-organizable dendronized polymers. This helical conformation mediates unprecedented functions. Self-organizable dendronized polymers have emerged as powerful building blocks for nanoscience by virtue of their dimensions and ability to self-organize. Discrete cylindrical and spherical structures with well-defined dimensions can be visualized and manipulated individually. More importantly, they provide a robust framework for elucidating functions available only at the nanoscale. This Account will highlight structures and functions generated from self-organizable dendronized polymers that enable integration of the nanoworld with its macroscopic universe. Emphasis is placed on those structures and functions derived from the induced helical backbone conformation of cylindrical self-organizable dendronized polymers.     

Toward understanding the effect of substitutes and solvents on entropic and enthalpic elasticity of single dendronized copolymers

Using single molecule force spectroscopy (SMFS), we have investigated the single chain elasticity of a series of dendronized copolymers, whose original backbone is styryl dendron and maleic anhydride. The amilysis reaction of maleic anhydride introduces amide and carboxyl side groups. Hence, the copolymer bears three type side groups, Fréchet type dendrons, amides and carboxyls. The single chain elasticity of the polymers in tetrahydrofuran (THF) and chloroform (CHCl₃) has been obtained, respectively. There is no hysteresis between the stretching and relaxing force curves of individual polymer chain, indicating that the elongation is carried out at the equilibrium condition. The force curves can be fitted well by the modified freely jointed chain model, which suggests that the elongation of the polymer chain is controlled by the entropic elasticity in the low-force region but dominated by enthalpic elasticity in the high-force region. The polymer with first-generation dendrons shows different elasticities in the two solvents, which should result from the different hydrogen bonds of the dendronized copolymer in two solvents. When the dendron groups are changed to be second and third generations, the single chain elasticity of the polymers is the same in two solvents. Hence, the elasticity of the polymer chain can be different depending on the properties of side groups and solvents.     

Synthesis and characterization of dendronized aromatic polyamides with bromomethyl groups in the periphery

This paper focused on the synthesis of novel functionalized dendronized aromatic polyamides, which contained a polyamide backbone and polyamide dendrons decorated with bromomethyl groups, by the macromonomer route. The new activating procedure of the synthesis of dendrons and macromonomers using thionyl chloride as an activating agent eliminated the protection/deprotection procedure and reduced side reactions. The structures of the dendrons, macromonomers, and polyamides were confirmed by FTIR, ¹H NMR, ¹³C NMR, and elemental analysis. The properties of the resulting dendronized polyamides, which were compared with that of the linear polyamide (LP), were studied using GPC, XRD, TGA, DSC, inherent viscosity measurement, and solubility experiment. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

醇酯型聚氨酯油墨连接料的研制

采用自制的不结晶型聚酯多元醇与含有侧链的扩链剂及异氰酸酯通过一步法反应制取醇酯型聚氨酯油墨连接料,分析了己二酸与间苯二甲酸二甲酯的物质的量比、聚酯多元醇的相对分子质量、扩链剂种类、R值、后熟化时间、溶剂配方对聚氨酯性能的影响。     

不同结构水性聚氨酯分散体的合成与性能研究

用不同结构不同分子质量的聚酯多元醇合成一系列水性聚氨酯分散体,探讨了其力学性能、黏度、粘附力和贮存稳定性,还分析了结晶性、扩链剂和硬段含量对水性聚氨酯性能的影响.结果表明,用PBA和PHA合成的水性聚氨酯具有较好的性能,适度的结晶性有利于提高粘附力,扩链交联剂在一定的比例范围才能保持分散液的稳定性,40%～46%硬段含量可以保证水性聚氨酯既有较好的力学性能和黏度,又有满足使用要求的干燥速度.     

Dendronized Polymer Architectures for Fuel Cell Membranes

Multi‐step synthetic pathways to low‐ion exchange capacity (IEC) polysulfone (PSU) with sulfonic acid functionalized aliphatic dendrons and sulfonated comb‐type PSU structures are developed and investigated in a comparative study as non‐fluorinated proton exchange membrane (PEM) candidates. In each case the side chains are synthesized and introduced in their sulfonated form onto an azide‐functionalized PSU via click chemistry. Three degrees of substitution of each architecture were prepared in order to evaluate the dependence on number of sulfonated side chains. Solution cast membranes were evaluated as PEMs for use in fuel cells by proton conductivity measurements, and in the case of dendronized architectures: thermal stability. The proposed synthetic strategy facilitates exploration of a non‐fluorous system with various flexible side chains where IEC is tunable by the degree of substitution.     

热致性液晶聚氨酯的合成研究

合成了两种含聚酯液晶基元的液晶聚氨酯,研究了反应时间、不同原料对产物结构的影响,利用红外光谱（IR）、偏光显微镜（POM）、差示扫描量热分析仪（DSC）等手段确认其结构,正交偏光场观察证实,该液晶聚氨酯在一定温度范围内为热致性向列型液晶。     

Polyurethane-modified polyester semi-interpenetrating networks

Four semi-interpenetrating polymer network materials based on a methyl acrylate modified crosslinked polyester and a polyurethane were synthesized and their dynamic mechanical and stress-strain properties were investigated. The tan δ-temperature dispersion of the semi-interpenetrating polymer network containing 70% polyurethane showed two maxima, while at 60% polyurethane a distinct shoulder is again to be seen at around the polyurethane glass transition temperature. At 30% and 50% by weight of polyurethane single, but rather broad, transitions occurred, despite the fact that at 30% and 60% polyurethane electron micrographs indicated a two-phase morphology. The stress at break was found to decrease approximately linearly with rubber content up to about 70% by weight.     

Facile synthesis of dendronized polyamides with chloromethyl groups in the periphery and some properties

A novel dendronized aromatic polyamide with a polyamide backbone and chloromethylene‐end‐functionalized polyamide dendrons is reported for the first time. An attempt at a one‐pot synthesis of end‐functionalized dendronized polymers with a macromonomer strategy without protection and deprotection procedures is also reported for the first time. The results from Fourier transform infrared and NMR spectral analysis indicated that perfect coverage of the chloromethyl groups in the periphery of the resulting polymers was obtained. Data from gel permeation chromatography analysis showed a typical weight‐average molecular weight (M_w) of 76,678 and a polydispersity of 2.44 for the first‐generation polymers and an M_w of 41,554 and a polydispersity of 2.74 for the second‐generation polymers. The solubility in solvents for the resulting polymers was improved remarkably because of the introduction of the dendritic fragments and the existence of the periphery functional groups. Both the glass‐transition temperature and onset decomposition temperature decreased versus those of the linear aromatic polyamides, but the 50% weight loss temperature was still up to 723°C. The X‐ray diffractograms indicated only an amorphous peak in the wide‐angle region of 24–25°. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

油墨用热塑性聚氨酯弹性体的研制

使用不结晶型的聚酯多元醇、扩链剂和异佛尔酮二异氰酸酯(IPDI)为主要原料,通过一步法反应制备出具有耐黄变、高光泽度、对低表面能材质有较高粘接强度的油墨用热塑性聚氨酯弹性体(TPU)。研究了聚酯多元醇、扩链剂种类和用量、催化剂种类和R值[n(-NCO)/n(-OH)]对TPU性能的影响,并对各种材质的粘接强度进行了测试。实验结果表明,当采用平均相对分子质量为1 500～2 000的自制聚酯多元醇、以氯化亚锡为催化剂、1,4-环己二甲醇(CHDM)为扩链剂且n(CHDM)∶n(聚酯多元醇)=0.5∶1、R=1.00～1.01时,制得的TPU对PET、PP和PE等低表面能材质具有良好的粘接性能。     

Analysis of reaction injection molding process of polyurethane-unsaturated polyester blends. Part II: Mechanical properties

The mechanical properties of polyurethane-unsaturated polyester interpenetrating polymer networks (IPNs) that were prepared by reaction injection molding (RIM) process were measured with variations In composition, cross-link density, and relative reaction rate. From dynamic mechanical analysis (DMA), it was found that the two component polymers had a good compatibility over the whole composition range. The tensile strengths of the blends were greater than those of the pure components and had a maximum value at 50/50 composition. The modulus of elasticity and surface hardness decreased and the impact strength increased as the polyurethane content was increased, but the changes were not high at low polyurethane content, below 50%. For higher cross-link density, the compatibility was enhanced and the mechanical properties were improved. When the reaction rates of the components were different, some extent of phase separation was found in DMA and the properties were affected adversely.     

Palladium Loaded Dendronized Polymer as Efficient Polymeric Sustainable Catalyst for Heck Coupling Reaction

Catalysis Letters - The palladium incorporated amine-functionalized dendronized polymer was synthesized by the addition of palladium acetate to dendronized polymer in methanol at room temperature....     

Preparation of an acrylics‐grafted polyester and its aqueous dispersion—mechanical properties of acrylics‐grafted polyesters

Mechanical properties of grafted polyesters were discussed. In the case of grafting of acrylics of more than 25% in the grafting product, mechanical properties of the grafting products decreased greatly compared with the raw polyester. The influence of the molecular structure of the grafted polyester was not observed. The effect of composition of the grafted polymers was discussed. Mechanical properties varied with the composition of the side chain. In the case of grafting onto aromatic polyesters, grafting of an aromatic unsaturated monomer improved the mechanical properties of the grafted polymer. On the other hand, in the case of grafting onto an aliphatic polyester, grafting of an aliphatic unsaturated monomer improved mechanical properties of the grafting polymer. We found that the grafting of the polymer having a high compatibility with the polyester improved the mechanical properties of the grafting products, from the determination of the compatibility of each polymer and the mechanical properties of the grafting products. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1149–1157, 2000     

弹性纤维熔纺聚合物研究的进展

介绍了非聚氨酯类、聚酯型聚氨酯类、聚醚型聚氨酯类聚合物及扩链剂在熔纺弹性纤维上的应用。指出 ,非聚氨酯类聚合物所熔纺的纤维具有较好的耐热性 ,耐氯性及定型性 ,弹性回复率较差 ,低于 95 %。用预聚体作交联剂的聚酯型聚氨酯熔纺纤维的弹性回复率高于前者 ,略低于聚醚型聚氨酯类。用芳香族二醇作扩链剂的聚醚型聚氨酯纤维 ,耐热性较好、弹性回复率较高 ,其性能接近溶液纺丝产品     

Synthesis and thermal properties of polyurethane–polysiloxane crosslinked polymer networks

Polysiloxane–polyurethane crosslinked polymer networks (PSI–PU) were synthesized in solution by polymerization of oligosiloxanes containing γ‐hydroxy propyl groups with polymethane polyphenyl polyisocyanate. Polyether‐based polyurethane and polyester‐based polyurethane were also prepared by a “one‐shot” method. Their thermal properties were studied by thermogravimetric analysis. It was observed that the thermal stability of PSI–PU was better than that of polyether‐based polyurethane and polyester‐based polyurethane, and an inert atmosphere had no effect on decomposition of polyurethanes below 350°C. It was found that polyurethane–polysiloxane crosslinked polymer networks decomposed slower in oxygen than in nitrogen in the temperature range of 350–550°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 310–315, 2003     

聚氨酯改性不饱和聚酯木器底漆的研究

为了提高不饱和聚酯木器底漆的低温打磨性,采用聚氨酯对不饱和聚酯进行改性,形成互穿聚合物网络(IPN)结构,通过IPN协同效应,结合聚氨酯涂料和不饱和聚酯涂料的优点,获得干燥速度快,易打磨,性能优异的漆膜,聚氨酯用量为30%～50%时效果最佳。     

具有良好耐MEK擦拭性能的聚氨酯卷材底漆的研制

制备了聚氨酯卷材底漆用聚酯树脂,探讨了具有不同端羟基数量的聚酯树脂、树脂与交联剂的质量比对聚氨酯卷材底漆及配套体系的耐MEK擦拭性能的影响。结果表明:提高聚酯树脂端羟基的数量可以在不影响柔韧性的条件下提高底漆的耐MEK擦拭性能;当树脂与交联剂的质量比为70∶30时配套体系的耐擦拭性能最佳,可以提高至200次。     

Synthesis, characterization and modification of azide-containing dendronized diblock copolymers

A series of dendronized diblock copolymers having rigid backbone and reactive surface were synthesized by ring-opening metathesis polymerization (ROMP) from dendronized norbornene derivatives using the second generation Grubb's catalyst. The bromine-terminated block of those rigid nanostructures has been converted to more reactive azide groups in one straightforward step. The resulting polymers were then functionalized by post-polymerization reaction with fullerene C₆₀ (electron acceptor) using thermal [3 + 2] cycloaddition reaction or with porphyrin (electron donor) using copper-catalyzed “click chemistry”, the ultimate goal being the preparation of efficient polymeric materials for photovoltaic applications. While fullerene addition was not complete (approximately 50%) because of cross-linking reactions and steric hindrance on the dendrimers surface, Zn-porphyrin introduction went to completion clearly demonstrating the usefulness of click chemistry for polymer functionalization.     

Effect of hydrophilic monomer on the surface properties of cationic polyurethane‐fluorinated acrylate hybrid dispersions

Cationic polyurethane‐fluorinated acrylate hybrid dispersions (PUFA) were prepared by the copolymerization of styrene, butyl acrylate, and 2,2,3,4,4,4‐hexafluorobutyl methacrylate in the medium of crosslinked polyurethane via phase inversion polymerization. The said polyurethane was synthesized in acetone from 2,4‐tolyene diisocyanate, N‐methyldiethanolamine, trimethylolpropane, and soft polyester diol block. The influences of hydrophilic monomer on the surface properties, immersion behaviors, particle size and, zeta potential of the dispersions were investigated. The results show that the addition of hydrophilic monomer can be advantaged to the stability of dispersions and yet will increase the surface free energy by more than 19.9%. The PUFA coating films cured at ambient conditions have the lower surface free energy (less than 0.02033 J/m²). At the same time, there is an obvious mobility of fluorinated groups in fluorinated polymer films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006