Synthesis and characterization of novel dendritic poly(ester‐amine) with peripheral hydroxyl

Dendritic poly(ester‐amine) with a peripheral hydroxyl [PEA(OH)] was synthesized from dendritic PEA terminated with acrylic double bonds [PEA(?)] and diethanolamine (DEA) by a Michael addition reaction. The effects of the reaction temperature, time, and solvent on the purities of PEA(OH) were studied. It was found that when the mole ratio of PEA(?) to DEA was 1:8 and the reaction was carried out in methanol at 25°C for 22 h, the purity of PEA(OH) was 94.6%. The structure of PEA(OH) was identified by IR, ¹H‐NMR, and elemental analysis. PEA(OH) is a surfactant and its aqueous form exhibits cloud points between the mass concentrations of 0.1 and 50 mass %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 60–64, 2005     

Curing of DGEBA epoxy resin by low generation amino‐group‐terminated dendrimers

Low generation amino‐group‐terminated poly(ester‐amine) dendrimers PEA1.0 (NH₂)₃ and PEA1.5 (NH₂)₈, and poly(amido‐amine) dendrimer PAMAM1.0 (NH₂)₄ were used as diglycidyl ether of bisphenol A (DGEBA) epoxy resin hardeners. Thermal behavior and curing kinetics of dendrimer/DGEBA systems were investigated by means of differential scanning calorimetry (DSC). Compared with ethylene diamine (EDA)/DGEBA system, the dendrimer/DGEBA systems gradually liberated heat in two stages during the curing process, and the total heat liberated was less. Apparent activation energy and curing reaction rate constants for dendrimer and EDA/DGEBA systems were estimated. Thermal stabilities and mechanical properties of cured thermosetting systems were examined as well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3902–3906, 2006     

Synthesis and characterization of hydroxypropyl terminated polydimethylsiloxane‐polyurethane copolymers

Polyurethane (PU) block copolymers were synthesized using prepared hydroxypropyl terminated polydimethylsiloxane (HTPDMS MW 990) and polyether diols (N‐210) as soft segment with 4,4′‐diphenylmethane diisocyanate (MDI) and 1,4‐butanediol. This low molecular weight polydimethylsiloxanes (PDMS) containing hydroxypropyl end‐groups displayed better compatibility with PU than common PDMS. In this article, we illustrate its synthesis routes and confirmed the proposed molecular structures using NMR and infrared radiation (IR). We varied the contents of HTPDMS and N‐210 in soft segments (HTPDMS—N‐210: 0 : 100, 20 : 80, 40 : 60, 60 : 40, 80 : 20, and 100 : 0) to synthesize a series of PDMS‐PU copolymer. IR spectroscopy showed the assignment characteristic groups of each peak in copolymers and confirmed that the desired HTPDMS‐PU copolymers have been prepared. The different thermal, dynamic mechanical and surface properties of the copolymers were compared by thermogravimetry, DMA, contact angle and solvent resistance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and application of polyoxyethylene‐grafted cationic polyamidoamine dendrimers as retention aids

Novel derivatives of fifth‐generation polyamidoamine, comprising polyoxyethylene macromonomer and acrylolyoxyethyl trimethylammonium chloride units, were synthesized. The polyoxyethylene‐grafted cationic polyamidoamine dendrimers were characterized with Fourier transform infrared, 1 H‐NMR, 13 C‐NMR, and elemental analysis. The synthesis recipes and properties of the dendrimers were studied. The retention efficiency of the dendrimers was determined and discussed. Highly effective retention aids were obtained in retention experiments with broadleaf wood pulp fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and characterization of amphiphilic PMTFPS‐b‐PEO diblock copolymers

A series of new amphiphilic poly[methyl(3,3,3‐trifluoropropyl) siloxane]‐b‐poly(ethyleneoxide) (PMTFPS‐b‐PEO) diblock copolymers with different ratio of hydrophobic segment to hydrophilic segment were prepared by coupling reactions of end‐functional PMTFPS and PEO homopolymers. PMTFPS‐b‐PEO diblock copolymers synthesized were shown to be well defined and narrow molecular weight distributed by characterizations such as NMR, GPC, and FTIR. Additionally, the solution properties of these diblock copolymers were investigated using tensiometry and transmission electron microscopy. Interestingly, the critical micellization concentration increases with increasing length of hydrophobic chain. Transmission electron microscopy studies showed that PMTFPS‐b‐PEO diblock copolymers in water preferentially aggregated into vesicles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of hydroxy‐terminated polyether‐polydimethylsiloxane‐polyether (PE‐PDMS‐PE) triblock oligomers and their use in the preparation of thermoplastic polyurethanes

A series of hydroxy‐terminated polyether‐polydimethylsiloxane‐polyether (α,ω‐dihydroxy‐(PE‐PDMS‐PE)) ABA triblock oligomers were synthesized from silanic fluids and methyl polyallyloxide polyethers. The reaction was a one‐step solventless hydrosilylation reaction with chloroplatinic acid (CPA) catalyst in the presence of heat. These ABA oligomers were characterized via ¹H‐NMR, ¹³C‐NMR, ²⁹Si‐NMR, FT‐IR, and GPC to demonstrate that they exhibit a 100% linear ABA structure with a siloxane Si? O chain in the center and polyether ethylene oxide (EO)/propylene oxide (PO) chains on the two sides terminated by hydroxy groups. The triblock oligomers were used to form thermoplastic polyurethanes (TPUs) using two‐step solventless bulk polymerization. The investigation of triblock oligomers impact on TPUs mechanical properties, thermal performance, surface water repellency, and morphology performance were analyzed by Instron material tester, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), water contact angles (WCA), scanning electron microscope (SEM), and transmission electron microscope (TEM). DSC and TGA indicated that PE‐PDMS‐PE modified TPUs had a clear lower T_g under ?120°C and the temperature of 50% weight loss was improved from 280 to 340°C. PE‐PDMS‐PE–modified TPU did not have the marked reduction on mechanical properties than pure polyether produced TPU. Tensile strength was maintained at 13 MPa and elongation was maintained at 300%. SEM and TEM were used to investigate the copolymers’ morphology performance and found that all PO PE‐PDMS‐PE had a pseudo‐three phase separation. WCA analysis confirmed that PE‐PDMS‐PE–modified TPU had significantly improved hydrophobic performance because the silicone structure linked into TPU copolymers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42521.     

Synthesis and characterization of poly(ether‐block‐amide) membranes for the pervaporation of organic/aqueous mixtures

We made poly(ether‐block‐amide) membranes by casting a solution on a nonsolvent surface. The effects of the solvent ratio (n‐butanol/isopropyl alcohol), temperature, and polymer concentration on the quality of the membranes were studied. The results show that the film quality was enhanced with increasing isopropyl alcohol ratio in the solvent. This behavior was related to the reduction of the solution surface tension and the interfacial tension between the solution and nonsolvent. Uniform films were made at a temperature range of 70–80°C and a polymer concentration of 4–7 wt %. The morphology of the membranes was investigated with scanning electron microscopy. The qualities of the films improved with increasing isopropyl alcohol ratio in the solvent. With these membranes, the pervaporation of ethyl butyrate (ETB)/water and isopropyl alcohol/water mixtures was studied, and high separation performance was achieved. For ETB/water mixtures, with increasing ETB content, both the permeation flux and separation factor increased. However, for isopropyl alcohol/water mixtures, with increasing isopropyl alcohol content, the permeation flux increased, but the separation factor was diminished. Increasing temperature in a limited range resulted in a decreasing separation factor and an increasing permeation flux. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis, excited state properties, and dynamic structural change of photoresponsive dendrimers

This article reviews recent advances in research of the dendrimer synthesis in connection with the design, synthesis and reaction of photoresponsive dendrimers. Dendrimers with photoreversible stilbene cores undergo mutual cis-trans isomerization in organic solvents to give photostationary state mixture of cis and trans isomers. Even the fourth generation (G4) stilbene dendrimer with molecular weight as high as 6500 underwent cis-trans photoisomerization within the lifetime of the excited singlet state. The large dendron group surrounding the photoreactive core may affect the excited state properties of the core to increase the efficiency of photoisomerization and/or decrease the fluorescence efficiency. The photochemistry of stilbene dendrimers with various types of dendron groups, and azobenzene dendrimers is discussed. Furthermore, recent advance of dendrimer syntheses and the possibility of their application to construct photoresponsive large molecules are discussed.     

Synthesis and characterization of epoxy/amine terminated amide‐imide‐imide blends

A new amine terminated amide‐imide (ATAI) was synthesized by the polycondensation reaction of tetrimide dicarboxylic acid containing bulky m‐chloro phenyl pendant with p‐phenylene diamine. The structure of all the prepared compounds were confirmed by FTIR,¹H‐NMR and ¹³C‐NMR techniques. This new diamine was then used to cure epoxy resin namely diglycidyl ester of bisphenol‐A and the cure reaction was studied by Differential scanning calorimetry. The cured blends show better thermal properties. The T_g of the epoxy resin was increased from 134°C to 156°C on addition of 6% of ATAI. The DMA results indicate that the polymer blend with 8% ATAI composition has higher storage modulus compared to 3% and 6% ATAI composition. The polymer blends with 3% and 6% ATAI composition have higher crosslinking density and lower intersegmental and intrasegmental friction coefficients than 8% ATAI composition. In the DMA curves an increase in the peak half‐width was observed with increasing ATAI composition, indicating the possibility of the existence of more than one phase with increasing ATAI concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of a carboxyl‐terminated waterborne hyperbranched polymer and its coordination behavior with chromium(III)

Despite its irreplaceable position in the leather industry, chrome tanning has been listed in the procession of limitation. The serious environmental pollution caused by chrome tanning through the residual chrome it leaves in wastewater has attracted great attention. To improve the absorption of chrome and reduce chromium emission, a novel hyperbranched ligand was synthesized and characterized. The impact elements of the coordination process between the hyperbranched oligomer and Cr(III) was investigated, and the characteristics of the complex are also discussed. This hyperbranched oligomer had a low molecular weight (weight‐average molecular weight = 2125) and narrow molecular weight distribution (PDI = 1.21). The time required for the coordination process between the hyperbranched oligomer and Cr(III) was around 6 h, and the optimum pH was 4.0. Moreover, the complex exhibited alkali resistance and fair resistance to oxidation; this suggested that this developed hyperbranched ligand is a potential masking agent or tanning auxiliary for chrome tanning and will enable improvements in chromium absorption. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40117.     

Synthesis and characterization of Schiff‐base‐containing polyimides

Benzyl bisthiosemicarbazone and its complexes with nickel (NiLH₄) and copper (CuLH₄) were used as diamine monomers for the synthesis of new Schiff‐base polyimides. The solution polycondensation of these monomers with the aromatic dianhydrides afforded metal‐containing Schiff‐base polyimides with inherent viscosities of 0.98–1.33 dL/g (measured in N‐methyl‐2‐pyrrolidone at 25°C). The polyimides were generally soluble in a wide range of solvents such as N,N‐dimethylformamide, N,N‐dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, tetrachloroethane, hexamethylene phosphoramide, N‐methyl‐2‐pyrrolidone, ethyl acetate, and pyridine at room temperature. The initial degradation temperatures of the resultant polyimides fell in the range of 220–350°C in nitrogen with char yields ranging from 36 to 64% at 700°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of platinum‐terminated dendritic carbosilane

Carbosilane dendrimers with peripheral allyl groups were synthesized from methyltrichlorosilane, allyl chloride and magnesium, and were then functionalized by binding aminopropyl groups. Periphery platinated complexes were synthesized from chloroplatinic acid and carbosilane dendrimers with aminopropyl groups. All compounds were characterized by ¹H NMR, ¹³C NMR, IR, GC‐MS, X‐ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP‐AES). Copyright © 2005 Society of Chemical Industry     

Synthesis and characterization of 4,4′‐diaminodiphenyl methane‐based benzoxazines and their polymers

A series of diamine‐based benzoxazine precursors have been prepared using 4,4′‐diaminodiphenyl methane, formaldehyde, and different phenol derivatives including phenol, p‐cresol, and 2‐naphthol. Their chemical structures were identified by FTIR, ¹H NMR, and elemental analysis. The curing reactions of those precursors were monitored by FTIR and DSC. The obtained materials exhibited higher glass transition temperature and char yields than the corresponding bisphenol‐A based polybenzoxazines. The polybenzoxazine prepared from phenol showed the highest char yields of 65% and thermal stability with 5 and 10% weight‐loss temperatures at 346 and 432°C, respectively. The polybenzoxazine prepared from 2‐naphthol exhibited the highest glass transition temperature at 244°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Rheological characterization of cellulose solutions in N‐methyl morpholine N‐oxide monohydrate

Three different modes of rheological properties were measured on 11 and 13 wt % solutions of cellulose in N‐methyl morpholine N‐oxide (NMMO) monohydrate, in which concentration range lyocell fibers of much reduced fibrillation are preferably produced. The dynamic rheological responses revealed that the Cox–Merz rule did not hold for these cellulose solutions. Both cellulose solutions showed a shear thinning behavior over the shear rate measured at 85, 95, 105, and 115°C. However, 13 wt % solution gave rise to yield behavior at 85ºC. The power law index ranged from 0.36 to 0.58. First normal stress difference (N₁) was increased with lowering temperature and with increasing concentration as expected. Plotting N₁ vs shear stress (τ_ω) gave almost a master curve independent of temperature and concentration, whose slope was about 0.93 for both cellulose solutions over the shear rate range observed (τ_ω > 500 Pa). In addition, the cellulose solutions gave high values of recoverable shear strain (S_R), ranging from 60 to 100. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 216–222, 2002     

Novel propargylether‐terminated monomers containing pyridine and phenyl pendent group: Synthesis,cure, and properties

Two novel propargylether‐terminated resins containing pyridine and bulky phenyl pendent group were prepared from propargyl bromide and different diphenols, and highly thermal stable polymers were obtained by the thermal cure of the monomers. The chemical structures of these novel monomers were well confirmed by FTIR, ¹H‐NMR and elemental analysis. Curing and thermal behavior of the resins were investigated using differential scanning calorimetry (DSC) and dynamic thermogravimetry in argon atmosphere. DSC curves of these two monomers showed a single endothermic peak corresponding to the conformation of chromene ring and homopolymerization of the chromene ring. The temperature at 5% weight loss (T_d5) was higher than 440°C under argon and the highest glass transition temperature (T_g) reached 362°C. The rheological behavior and solubility of the monomer were also investigated. The monomers showed excellent flow‐ability, broad processing window, and great solubility. These results showed that the two resins could be ideal candidates for high‐temperature resistant resins. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40469.     

Epoxide‐terminated hyperbranched polyether sulphone as triple enhancement modifier for DGEBA

Epoxide‐terminated hyperbranched polyether sulphones (EHBPESs) with different backbone structures were synthesized and used as tougheners for diglycidyl ether of bisphenol‐A (DGEBA) curing system, which result in nonphase‐separated cured networks. Effects of backbone structure (at comparable degree of polymerization) and loading contents on the mechanical and thermal properties of cured hybrids were investigated. The hybrid containing EHBPES3, which has the most flexible backbone, shows the best mechanical performance and highest glass transition temperature (T_g). Compared with unmodified system, the impact strength, tensile strength, elongation at break of the hybrid containing 5% EHBPES3 increased by 69.8%, 9.4%, and 60.2%, respectively. The balanced improvements were attributed to the increased crosslink density and fractional free volume as well as the unique inhomogeneous network structure because of incorporation of hyperbranched modifiers with proper structure and loading contents. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41910.     

Synthesis and characterization of graft copolymer of polyacrylonitrile‐g‐polyethylene glycol‐maleic acid monoester macromonomer

A novel solid–solid phase‐change energy storage material was synthesized by the aqueous phase precipitation polymerization. The amphiphilic polyethylene glycol‐maleic acid monoester macromonomer (MAPEG) with a double bond and a terminal carboxyl was the side chain and the polyacrylonitrile (PAN) was a skeleton. The chemical structure and thermal properties of the graft copolymer were investigated. The results indicated that the MAPEG chains were successfully grafted onto the PAN backbone. The graft copolymer possess good thermal reliability and the phase‐transition temperature is in the temperature range of human comfort, meanwhile, the melting enthalpy could reach 74.16 J/g and the crystallization enthalpy could reach 65.40 J/g, accounting for theoretical enthalpy value of 89 and 93%, respectively. Besides, optimum conditions of synthesizing the graft copolymer were determined by orthogonal experiment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40152.     

Investigation of allyl‐capped carbosilane dendrimers used as crosslinker for silicone rubber

High‐temperature vulcanized silicone rubber was prepared by using allyl‐capped carbosilane dendrimers, in which the core molecules were Si(CH₂CH?CH₂)₄ and Ph₂Si(CH₂CH?CH₂)₂ as crosslinker and nanoscale reinforcing filler, respectively. Allyl‐capped carbosilane dendrimers improved the mechanical properties of silicone rubber. The optimum tensile strength and tear strength were 9.6 MPa and 31.0 kN/m, respectively, when using SiG_n(allyl)m as the crosslinker and 10.1 MPa and 32.0 kN/m, respectively, when using Ph₂SiG_n(allyl)m as the crosslinker. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1772–1775, 2006     

Synthesis and characterization of ethoxy‐terminated ladder‐like polymethylsilsesquioxane oligomer

A fully ethoxy‐terminated ladder‐like polymethylsilsesquioxane oligomer (EtO‐Me‐T) has been synthesized and characterized for the first time using an effective transient catalyst (tetramethylammonium hydroxide, TMAH) via the dehydration alcoholysis reaction of hydroxy‐terminated ladder‐like polymethylsilsesquioxane (HO‐Me‐T) prepared by a modified stepwise coupling polymerization approach. Compared with the common acidic or basic catalysts, use of the transient catalyst TMAH can not only make the HO‐Me‐T molecules fully ethoxy‐terminated but also enables the catalyst to be readily and thoroughly removed after completion of the alcoholysis reaction. It is noteworthy that the common acidic or basic catalysts widely used in the dehydration alcoholysis reaction are clearly unsuitable for the preparation of EtO‐Me‐T oligomer because the latter would be hydrolyzed unavoidably back to the parent HO‐Me‐T during the washing process. In addition, preliminary exploration indicates that, when compared with the tetraethyl orthosilicate (Si(OEt)₄) generally used as a crosslinking agent for the room‐temperature vulcanization of silicone rubber (RTV‐SR), the oligomer EtO‐Me‐T is a promising replacement which can greatly improve the mechanical properties of RTV‐SR Copyright © 2003 Society of Chemical Industry