Synthesis and Characterization of Hyperbranched Linear Surfactants

A series of hyperbranched linear surfactants (HLS) was prepared by using oleic acid modifying the first generation hydroxyl-terminated hyperbranched polymer (HBP-1), which was obtained through a step synthesis method using trimethylolpropane and N,N-dihydroxyethyl dodecylamine -3-amine-methyl propionate (AB₂-type monomer). AB₂—type monomer was obtained through the Michael addition reaction of methyl acrylate and diethanol amine. Single-factor experiments were conducted to investigate the influences of reaction conditions such as temperature, oleic acid dosage, and reaction time on the synthesis of HLS. Results indicate that the optimal temperature and time of the esterification reaction were 130 °C and 3 h, respectively. The structures of HLS were characterized by Fourier transform infrared spectrophotometry (FT-IR) and the results indicate that HBP-1 had been successfully modified by oleic acid. Furthermore, the surface tension and the critical micelle concentration (CMC) of the HLS solution show that HLS can significantly reduce the surface tension of water.     

Monolayer and bilayer conducting polymer coatings for corrosion protection of steel in 1 M H2SO4 solution

In this study, monolayer polypyrrole (PPY), polyaniline (PANI), and bilayer PPY/PANI, PANI/PPY coatings were deposited onto steel electrodes by electropolymerization in 0.1 M monomer and 0.3 M oxalic acid solution. Such corrosion parameters of these electrodes, as corrosion potentials, anodic Tafel constants and corrosion current densities were determined by means of current–potential curves as a function of time in 1 M H₂SO₄ solution. These findings were compared to the corrosion parameters of a bare steel electrode in the same acid solution. The monolayer and bilayer polymer coatings were characterized by the Fourier transform infrared (FTIR) spectroscopy and SEM. Bilayer coatings displayed better corrosion inhibition efficiencies than monolayer coatings. Furthermore, the PPY/PANI coatings offered superior corrosion protection than the PANI/PPY coatings.     

Nonisothermal crystallization kinetics of AB2 hyperbranched polymer‐filled polypropylene

In this article, nonisothermal crystallization kinetics of polypropylene (PP) and AB₂ hyperbranched polymer (HBP)‐filled PP have been investigated by differential scanning calorimetry. The Avrami analysis modified by Mandelkern and a method combined with Avrami and Ozawa equations were employed to describe successfully the nonisothermal crystallization kinetics of samples. The conclusion showed that HBP can prompt crystallization effectively. Furthermore, in blends of different HBP contents, the value of t_1/2 became smaller with increasing HBP content; however, the crystallization rate of the blend decreased slightly when content of HBP is 5%. An increase in the Avrami exponent showed that addition of HBP influenced the mechanism of nucleation and the growth of PP crystallites. The possible explanation could be attributed to the fractal structure of HBP. The polarized micrographs showed that HBP acts as a heterogeneous nucleation agent, and the nucleation efficiency has increased remarkably in HBP/PP blends. POLYM. ENG. SCI., 53:2535–2540, 2013. © 2013 Society of Plastics Engineers     

Synthesis of Gemini‐Like Methyl Acrylate‐Acrylic Acid‐Methyl Acrylate Triblock Copolymers Surfactants by RAFT Polymerization in Solution and Investigation of their Behavior at the Air–Water Interface

A series of methyl acrylate‐acrylic acid amphiphilic triblock copolymers (PMA‐PAA‐PMA) were prepared by solution polymerization using S,S′‐bis (α,α‐dimethy1acetic acid) trithiocarbonate (BDAT) as a reversible addition fragmentation chain transfer (RAFT) agent and methyl acrylate (MA) as the first monomer. The triblock copolymers and their common MA homopolymer precursors were characterized in terms of their compositions, molecular weights and behavior at the air–water interface using ¹H‐NMR spectroscopy, thermogravimetric analysis, gel permeation chromatography, surface tension, transmission electron microscopy (TEM) and dynamic light scattering respectively. The results indicated that PMA‐PAA‐PMA was successfully synthesized through RAFT polymerization. The polydispersity index (PDI) decreased when the molar ratio [n(MA)/n(AA)] increased, the lowest PDI was obtained at 5.23 wt% RAFT and the molecular weights were consistent with the theoretical value as the RAFT agent percentage varied. The polymer neutralized by sodium hydroxide solution shows a low critical micelle concentration (CMC), which was <10^?2 mol L^?1 in water. The A_min values increased and showed a maximum with decreased AA chain length. TEM showed that the neutralized polymer formed a special vesicle structure with large pore structure which led to a low CMC and surface tension of water.     

Toughening of an epoxy anhydride resin system using an epoxidized hyperbranched polymer

This paper reports on the use of an epoxidized hyperbranched polymer (HBP) as an additive to an epoxy anhydride resin system. The hyperbranched polymer used was an aliphatic polyester with a molecular weight of around 10 500 g mol^?1. The epoxy resin mixture used was a combination of a difunctional diglycidyl ether of bisphenol A (DGEBA) epoxy and an epoxy novolac, and was cured with a catalysed anhydride curing agent. It has been shown that, at a concentration range of 0 to 20 wt% addition, the HBP is able to almost double the fracture toughness, with little evidence of any deleterious effects upon processing and the durability of the cured resin system. The flexural modulus and stress, however, were found to both decrease by about 30% as a result of HBP addition while the T_g was found to decrease by about 10%. The processability of the uncured resin systems has been investigated by using rheological and calorimetric techniques and it was found that the processability window, as determined by the gel time and viscosity changes, was relatively unaffected by HBP addition. The fracture surfaces were evaluated by using scanning electron microscopy which showed that the unique structure of the HBP facilitates an enhanced interaction with the polymer matrix to achieve excellent toughness enhancement of the polymer matrix. The durability of the epoxy network has been investigated via thermogravimetric analysis (TGA) and solvent uptake, and the HBP has been shown to have little systematic deleterious effect upon the degradation temperatures and the total amount of solvent absorbed. Copyright © 2003 Society of Chemical Industry     

The structure and application of amine‐terminated hyperbranched polymer shale inhibitor for water‐based drilling fluid

Amine‐terminated hyperbranched polymer (HBP‐NH₂), as an inhibitor in water‐based drilling fluid, is prepared by the polycondensation of diamine AB₂ monomers. The primary amine and secondary amide structures are confirmed by Fourier transform infrared spectroscopy and nuclear magnetic resonance hydrogen spectroscopy. Through time of flight mass spectrometry, the molecular weight of HBP‐NH₂ is mainly distributed in the range of 200–1400. Also, the quasi‐spherical shape and the high temperature resistance (200 °C) performance of HBP‐NH₂ are, respectively, certified through the environmental scanning electron microscope and the thermogravimetric analysis. In the inhibition performance test, the linear expansion rate of sodium bentonite in 3 wt % HBP‐NH₂ aqueous solution is only 11.42%, which is lower than other inhibitors (KCl, FA‐367, and HPAM). Zeta potential analysis shows that HBP‐NH₂ has a strong ability to inhibit the hydration and dispersion of sodium bentonite by protonated primary amine groups. Compared with the base slurry, the absolute value of zeta potential is reduced by 25.5 mV in the slurry containing 3 wt % HBP‐NH₂ at 180 rpm. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45466.     

Solubilization of single-walled carbon nanotubes by entanglements between them and hyperbranched phenolic polymer

Hyperbranched phenolic polymer (HBP) was prepared by Lewis acid-catalyzed polycondensation of bifunctional phenolic monomer with trifunctional phenolic monomer. By choosing an appropriate Lewis acid, HBP was successfully obtained. By using physical adsorption of HBP on a single-walled carbon nanotube (SWCNT) surface, solubilization of SWCNTs was examined. SWCNTs were soluble with extended branches of HBP in N,N-dimethylformamide (DMF) solution, while they were insoluble in a linear phenolic polymer. In the presence of shrinking branches of HBP in tetrahydrofuran, SWCNTs were hardly soluble. Entanglements between extended branches of HBP and SWCNT in DMF solution resulted in high solubility of SWCNTs.     

Synthesis and characterization of leather impregnated with bismaleimide (BMI)–Jeffamine® resins

Leather/polymer composites were prepared by impregnating chrome-tanned cattlehide with a solution containing 1,1′-(methylenedi-4,1-phenylene)bismaleimide and Jeffamine® D-230. The mechanical properties in tension, glass transition temperatures, dynamic storage moduli, and moisture absorption of the composites were measured. Impregnated samples showed significant changes in tensile properties, such as the Young's modulus and strain at break, when compared with chrome-tanned cattlehide. In addition, impact energy increased significantly upon formation of the leather/polymer composite over that of the bismaleimide–Jeffamine® resin itself. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1019–1027, 1998     

Cyclodextrin-based hyperbranched polymers by acyclic diene metathesis polymerization of an AB<Subscript>n</Subscript> monomer: molecule design,synthesis, and characterization

A novel cyclodextrin-based hyperbranched polymer (HBP) was synthetized via acyclic diene metathesis (ADMET) polymerization in homogeneous water/organic mixtures. A modified α-cyclodextrin (α-CD) molecule with one electron-rich terminal alkene and many electron-poor acrylates was first prepared through the esterification reaction, and then utilized as an AB_n-type monomer for subsequent ADMET polymerization between alkene and acrylate using the second generation Hoveyda-Grubbs catalyst, yielding HBP with the reaction time prolonged. The chemical structures of monomer and HBP were characterized by elemental analysis, IR, gel permeation chromatography with multiangle laser light scattering, and NMR measurements. The degree of branching was determined by using ¹H NMR spectroscopy and the values ranged from 0.51 to 0.42. Influence of the molecular weight on the properties (thermal stability and solubility) was also investigated. The resulting HBPs showed the good thermal stability, and higher molecular weight resulted in higher decomposition temperature from 361 °C to 383 °C. These thermally stable HBPs also displayed the excellent solubility in aprotic polar solvents.     

Isothermal crystallization kinetics of AB<Subscript>3</Subscript> hyperbranched polymer (HBP)/polypropylene (PP) blends

In this paper, the isothermal crystallization kinetics of pure isotactic polypropylene (iPP) and iPP with 5% AB₃ hyperbranched polymer (HBP) added had been investigated by differential scanning calorimetry (DSC). During isothermal crystallization, the crystallization rate of the blends was higher than those of iPP remarkably. Moreover, the value of t _½ became smaller with increasing the HBP molecular weight in blends, however, the crystallization rate of the blend decreased when the higher molecular weight HBP (\( \bar{M}_{n} \) = 12,500) was added. The crystallization rate of the blends was more sensitive to temperature than that of iPP. An increase in the Avrami exponent may be attributed to the fractal structure of hyperbranched polymer.     

Effect of crystallinity on surface morphology and light transmittance of poly(vinylidene fluoride‐co‐hexafluoropropylene) thin film

Homopolymer of vinylidene fluoride and its copolymers containing hexafluoropropylene (HFP) were prepared from free radical solution polymerizations and spin‐coated on the glass slides to fabricate thin film with a thickness of ～ 1 μm. It was found that the surface morphology of fluorinated thin films was strongly dependent on the crystallinity of polymers. In addition, the surface morphology was the most important factor to determine the optical transmittance of glass coated with the fluoropolymer thin film. As decreasing the crystallinity of the polymer by introducing HFP with a bulky CF₃ moiety, the surface of thin film became flattened and the transmittance of visible light was increased by reducing scattering. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A novel amphiphilic AB2 star copolymer synthesized by the combination of ring-opening metathesis polymerization and atom transfer radical polymerization

A new amphiphilic AB₂ star copolymer was synthesized by the combination of ring-opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP). Two different routes (methods A and B) were employed firstly to prepare the poly(oxanorbornene)-based monotelechelic polymers as the hydrophobic arm bearing dibromo-ended group via ROMP in the presence of two different terminating agents catalyzed by first generation Grubbs catalyst. The values of capping efficiency (CE) of the polymers were determined by NMR, which were 94% and 67% for methods A and B, respectively. Then, the dibromo-ended ROMP polymers were used as the macroinitiators for ATRP of 2-(dimethylamino)ethyl methacrylate (DMAEMA) to produce two hydrophilic arms. The prepared amphiphilic AB₂ star copolymers poly(7-oxanorborn-5-ene-exo,exo-2,3-dicarboxylic acid dimethyl ester)-block-bis[poly(2-(dimethylamino)ethyl methacrylate)] (PONBDM_n-b-(PDMAEMA_m)₂) with a fixed chain length of hydrophobic PONBDM and various hydrophilic PDMAEMA chain lengths can self-assemble spontaneously in water to form polymeric micelles, which were characterized by dynamic light scattering, atom force microscopy, and transmission electron microscopy measurements.     

Designing maleic anhydride-α-olifin copolymeric combs as wax crystal growth nucleators

Modification of the wax crystal habit is of great practical interest during transportation and processing of crude oil at low temperature. Various pour point depressant (PPD) additives can facilitate this modification by different mechanisms. Comb shaped polymer additives are known to depress the pour point of crude oil by providing different nucleation sites for the precipitation of wax. This paper describes performance based design, synthesis, characterization and evaluation of comb shaped polymeric diesters. Copolymers of maleic anhydride with different unsaturated C₂₂ esters were synthesized and copolymers then reacted with two unsaturated fatty alcohols. All products were characterized by Fourier Transform Infra Red (FTIR) spectroscopy and Gel Permeation Chromatography (GPC). Rheological properties of crude (with and without additive) were studied by Advance Rheometer AR-500. In this study the additive based on oleic acid was evaluated as good PPD and rheology modifier.     

Simultaneous novel synthesis of conducting,nonconducting, and crosslinked polymers by microwave initiation

A novel synthesis of poly(dibromophenylene oxide) (P), conducting polymer (CP), and/or crosslinked polymer (CLP), and/or radical ion polymers (RIP) was achieved simultaneously from sodium 2,4,6‐tribromophenolate by microwave energy in a very short‐time interval. The synthesized polymers were characterized via elemental analysis, FTIR, ¹H NMR and ¹³C NMR, X‐ray diffraction spectroscopy, SEM, DSC, TGA, ESR, GPC, conductivity measurement, and light scattering. It was found that polymerization proceeds through both 1,2‐ and 1,4‐addition at equal rates. The effects of the energy and time on the % conversion and the polymer synthesis were investigated. The optimum condition for synthesis of P (the highest M_w, 2.97 × 10⁵ g/mol) and CP was 70 W for 5 min in 5 mL water and 100 W for 1 min in 0.5 mL water, having maximum values 23.6% and 27.2%, respectively. In addition, synthesis of CLP and RIP were achieved in 5 mL water at 350 W and 700 W at the end of 1 min, respectively. The direct synthesis of highly conducting polymer, with the conductivity of 1 S cm^?2 was achieved in the absence of applied doping process in a very short time sequence. P, CP, CLP, and RIP had fine granular, sponge‐like, dendrite, and coarse surface structures, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5427–5435, 2006     

Polymer gel electrolytes prepared from P(EG‐co‐PG) and their nanocomposites using organically modified montmorillonite

Polymer gel electrolytes were prepared by thermal crosslinking reaction of a series of acrylic end‐capped poly(ethylene glycol) and poly(propylene glycol) [P(EG‐co‐PG)] having various geometries and molecular weights. Acrylic end‐capped prepolymers were prepared by the esterification of low molecular weight (M_n: 1900–5000) P(EG‐co‐PG) with acrylic acid. The linear increase in the ionic conductivity of polymer gel electrolyte films was observed with increasing temperature. The increase in the conductivity was also monitored by increasing the molecular weight of precursor polymer. Nanocomposite electrolytes were prepared by the addition of 5 wt % of organically modified layered silicate (montmorillonite) into the gel polymer electrolytes. The enhancement of the ionic conductivity as well as mechanical properties was observed in the nanocomposite systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 894–899, 2004     

高性能聚羧酸减缩材料的研发(Ⅲ)——高分子聚合物(HP-SRA)的作用机理

通过对比,研究了采用自行研发的高分子聚合物(HP-SRA)与Eclipse-Floor减缩剂(Eclipse-SRA)2种减缩材料在降低水泥颗粒表面上的平均吸附率、溶液表面张力和蒸发速率、提高溶液动力黏度、减少水泥砂浆收缩和改善孔结构分布等方面的作用。结果表明,水泥颗粒表面对高分子聚合物(HP-SRA)的平均吸附率小于10%;高分子聚合物(HP-SRA)可显著降低溶液表面张力和蒸发速率,大幅提高溶液动力黏度;高分子聚合物(HPSRA)对水泥砂浆减缩效果显著,在其掺入量为0.30%(质量分数)时,水泥砂浆在3 d和28 d养护龄期时的收缩率分别下降了48.6%和20.2%。     

Synthesis of hyperbranched aromatic polyamide–imide and its grafting onto multiwalled carbon nanotubes

A flexible hyperbranched aromatic polyamide–imide (PAI) having an amine group in the center and carboxyl groups in the ends was synthesized from a AB₂ type of monomer of 2‐(6‐aminohexylcarbomoyl) terephthalic acid that was prepared from trimellitic anhydride and 1,6‐diaminohexane. Fourier transformed infrared spectra (FTIR), NMR, and ES‐MS were used to characterize the structure of the monomer and the synthesized hyperbranched polymer. Then the hyperbranched PAI was grafted onto the multiwalled carbon nanotubes (MWNTs) that was first treated by acid and changed into MWNT‐COCl by SOCl₂ in a tetrahydrofuran solution. By observation with transmission electron microscopy and characterization with FTIR and thermal gravity of analysis, the functionalized MWNTs were terminally enclosed with polymer; it was believed that the MWNTs were linked with a big carboxylic claw at the end and the adsorption ability of the MWNTs to NH₂‐substrate was enhanced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of amphiphilic copolymer containing ruthenium tris(bipyridyl) photosensitizer on the formation of honeycomb-patterned film

A new functional amphiphilic polymer (A_P) containing ruthenium tris(bipyridyl) photosensitizer was synthesized and a honeycomb-patterned film was fabricated by casting a polystyrene solution and different concentrations of A_P under humid conditions. The amphiphilic copolymer was obtained by the radical copolymerization of ruthenium (4-vinyl-4′-methyl-2,2′-bipyridine)bis(2,2′-bipyridine)bis(hexaflurophosphate) with N-dodecylacrylamide and N-isopropylacrylamide. Without the addition of A_P, irregularly ordered porous films were obtained, while adding A_P in the casting solution resulted in highly ordered honeycomb-patterned films. In addition, the pore diameter and height of the porous structure increased with the increase of A_P amount in the solution. However, an excessive amount of A_P induced an irregularly structured pattern with small pore sizes.     

Low pressure hydride anode materials for rechargeable batteries

AB₅-type intermetallic compounds were prepared by induction melting. Electrodes were fabricated from metal powders by addition of a polymer binder and pressing at ambient temperature. Subsequently the electrodes were activated by amperodynamic cycling. Specific electrochemical experiments including rest potential measurements and potential controlled charge/discharge cycles were carried out to determine the thermodynamic and kinetic properties. The commonly used method for the determination of pressure-concentration isotherms was replaced by an electrochemical method. Potential measurements were carried out under equilibrium conditions at different states of charge enabling the calculation of pressure-composition isotherms from these data.     

Polymorphism and spherulite morphology of poly(1,4‐butylene adipate)/organically‐modified layered double hydroxide nanocomposites

A novel biodegradable poly(1,4‐butylene adipate)/organically‐modified layered double hydroxide (PBA/m‐LDH) nanocomposites are synthesized using the solution mixing process. The m‐LDH is originally prepared with magnesium nitrate hexahydrote (Mg(NO₃)₂ 6H₂O), aluminum nitrate‐9‐hydrate (Al(NO₃)₃ 9H₂O), oleic acid, and sorbitol by a novel one‐step co‐precipitation method to intercalate the organo‐modifier of oleic acid and sorbitol into the interlayer of LDH. The structure and morphology of the PBA/m‐LDH nanocomposites are characterized using X‐ray diffraction and transmission electron microscopy (TEM). It has been shown that the m‐LDH is exfoliated and well distributed in PBA matrix. The effect of m‐LDH on the polymorphic crystal and morphology of PBA at various crystallization temperatures (T_cs) would be investigated using WAXD and POM. Both data indicate that the addition of m‐LDH can change the starting formation temperature of α‐form crystals. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42526.