Synthesis and characteristics of pectiniform polyurethane‐modified polycarboxylate at room temperature

In this article, modified polyurethane prepolymer was synthesized by segmental synthesis method using isophorone diisocyanate, hydroxyl‐terminated silicone, polyether glycol dimethylolpropionic acid as raw materials. After that, pectiniform polycarboxylate, of which side chains were in roughly the same polymerization degree and main chains were in different lengths, was synthesized at room temperature in initiation system of hydrogen peroxide, ascorbic acid, and persulfate. Moreover, influence of various factors on the synthesis of polyurethane‐modified polycarboxylate at room temperature was discussed in detail and optimal synthesis process was determined. Results showed that redox initiation system, increasing initiator and monomer concentration, and extending reaction time needed to be adopted to complete the reaction. However, when the reaction time was over 4 h, water reducing of polycarboxylate declined rapidly. In addition, it could be found in Fourier transform infrared spectrum analysis that the ? C?C? double bonds in acrylic acid were opened and polymerized, macromolecular chain segments were successfully connected to polyoxyethylene chain segment, and resulting polycarboxylic acid molecule contained hydroxy, carboxyl, methyl, ester group, and other groups. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45873.     

Structure characterization and adsorption properties of tetraethylenepentamine ion exchange fiber

A novel tetraethylenepentamine ion exchange fiber (TAIEF) was prepared using polypropylene grafted styrene (PP‐g‐ST) fiber as raw material. The chemical structure of TAIEF was characterized using infrared spectrum (IR) method. TAIEF had good appearance and shape after reaction in SEM images, the TGA curves revealed that both PP‐g‐ST fiber and acetyl PP‐g‐ST fiber had good thermal stability below 250 °C, and the weight loss rate of TAIEF is 9% from 50 °C to 200 °C obtained by TGA. TAIEF adsorption capacity to Fe(III) is larger than that of In(III) in the pH value 1.00 to 3.00, while the pH value is at 2.50 to 3.00, TAIEF adsorption capacity to Fe(II) and Zn(II) are smaller than that of In(III). The selective adsorption ability to Fe(III) is higher than In(III), and the selective absorptivity to In(III) is better than Fe(II) and Zn(II). The mechanism was explained of TAIEF favorable selective adsorption to In(III) and Fe(III) ions in mixed solutions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44513.     

聚羧酸减水剂在水泥颗粒表面的吸附行为

合成一系列聚羧酸减水剂,探讨不同单体摩尔比对其吸附性能的影响。结果表明,当n(烯丙醇聚氧乙烯醚)∶n(2-丙烯酰胺-2-甲基丙磺酸钠)∶n(丙烯酸)∶n(马来酸酐)=1∶0.14∶3.6∶2.6时,产物吸附性能最优。并利用总有机碳分析技术,研究了不同温度、不同浓度下最优产物在水泥颗粒表面的吸附动力学和热力学。动力学研究结果表明：聚羧酸在水泥颗粒表面的吸附过程符合Lagergren吸附速率方程,吸附速率常数k=0.01594 min-1(30℃),表观活化能Ea=17.9647 kJ·mol-1。热力学研究结果表明：随温度升高,聚羧酸在水泥颗粒表面的吸附量增大;求得吸附热力学参数分别为ΔHad=-24.788 kJ·mol-1,ΔSad=0.050 kJ·mol-1·K-1,ΔGad=-39.886 kJ·mol-1(30℃),可知该吸附过程是自发的放热反应。理论上温度升高对吸附不利,但因放出的热量促进水泥水化,导致聚羧酸分子容易掺杂到水化产物中,从而使更多聚羧酸吸附到水泥颗粒表面,令其吸附量反而增大。     

Synthesis of thermoresponsive copolymer/silica-coated magnetite nanoparticle composite and its application for heavy metal ion recovery

To enhance chemical stability and suppress of aggregation of magnetite nanoparticles (MNPs), which are used as a support for thermoresponsive copolymer immobilization, silica coating of the MNPs is applied via the electrooxidation method. Although the resulting silica coated-MNPs also formed aggregates, the size distribution of the aggregate shifted to smaller size range. Because of that, the surface area available for copolymer immobilization increased approximately 6.7 times at maximum as compared with that of the uncoated MNPs. It contributed to the increase of the amount of the immobilized copolymer on the silica-coated MNPs, which is approximately four times larger than that on the uncoated MNPs. Fe₃O₄ dissolution test confirmed enhancement of chemical stability of MNPs. The thermoresponsive copolymer immobilized on the silica-coated MNPs shows the ability to recycle Cu(II) ion from Cu(II) containing solution by changing temperature with significantly shorter time than those in other thermoresponsive adsorbents in gel form.     

Photo-grafting of β-cyclodextrin onto the polyethersulfone microfiltration-membrane: Fast surface hydrophilicity improvement and continuous phthalate ester removal

This work presents a facile, fast, and green approach for the production of a novel glycidyl methacrylate-β-cyclodextrin grafted polyethersulfone membrane (GMA-β-CD-PESm). Firstly, glycidyl methacrylate-bonded β-cyclodextrin (GMA-β-CD) is synthesized and then it is photografted onto the polyethersulfone (PES) membrane. The effects of ultraviolet radiation time, GMA-β-CD concentration, modification techniques, and degrees of substitution are studied. The results indicated that, with altering of studied parameters, membranes with degree of grafting 50–3000 μg/cm² are obtained. The prepared membranes are characterized by attenuated total reflection Fourier transform infrared spectroscopy, SEM, and contact angle (CA) measurements. The CA measurements confirmed that hydrophilicity of the membrane significantly increased by grafting of GMA-β-CD onto the PES membrane. The CA angle is decreased from 64° in the neat PES to 39.4° in GMA-β-CD-PESm. The results of microfiltration show that GMA-β-CD-PESm have a good potential to continuous adsorbing and removing of di(2-ethylhexyl) phthalate from aqueous solutions. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47632.     

Synthesis and characterization of eugenol-based silicone modified waterborne polyurethane with excellent properties

A eugenol-based silicone-containing monomer 4,4′-(1,1,3,3-tetramethyldisiloxane-1,3-dipropyl)bis-2-methoxyphenol(EUSi) was synthesized from eugenol and 1,1,3,3-tetramethyldisiloxane via the hydrosilylation reaction. And waterborne polyurethane (WPU) with excellent properties was obtained by using EUSi as a type of diol chain extender. The unique combination of rigidity and flexibility in the chemical structure of EUSi greatly facilitated the mechanical properties, thermal properties, and water resistance of WPU. With only a 3% dosage of EUSi, the maximum tensile strength was increased from 6.2 to 22.4 MPa, while the water absorption was decreased from 31.3% to a surprisingly 7.6%. Our work provides a new convenient strategy for the preparation of organosilicon-modified WPU with improved performance.     

微波作用下酰胺型聚羧酸减水剂的合成及其性能研究

在微波作用下,以自制活性大单体聚乙二醇丙烯酸酯(PEGAA)、马来酸酐(MAH)、丙烯酰胺(AM)及甲基丙烯磺酸钠(SMAS)为主要原料,过硫酸铵(APS)为引发剂,制备性能优异的酰胺型聚羧酸减水剂,考察各单体用量、微波功率、反应时间等因素对减水剂性能的影响。结果表明,合成酰胺型聚羧酸减水剂最佳工艺为:n(MAH)∶n(PEGAA)∶n(SMAS)=2.5∶1∶0.5,AM、APS质量分数分别为反应物总质量的9%和4%,微波功率300 W及反应时间25 min。与传统的水浴相比,该工艺高效、节能,产品性能优异,在聚羧酸减水剂掺量0.5%条件下,水泥净浆流动度达275 mm,砂浆减水率32.5%,且前期具有缓凝作用,后期对胶砂抗压强度增强显著,具有良好的工业应用前景。     

微波作用下酰胺型聚羧酸减水剂的合成及其性能研究

在微波作用下,以自制活性大单体聚乙二醇丙烯酸酯(PEGAA)、马来酸酐(MAH)、丙烯酰胺(AM)及甲基丙烯磺酸钠(SMAS)为主要原料,过硫酸铵(APS)为引发剂,制备性能优异的酰胺型聚羧酸减水剂,考察各单体用量、微波功率、反应时间等因素对减水剂性能的影响。结果表明,合成酰胺型聚羧酸减水剂最佳工艺为:n(MAH)∶n(PEGAA)∶n(SMAS)=2.5∶1∶0.5,AM、APS质量分数分别为反应物总质量的9%和4%,微波功率300 W及反应时间25 min。与传统的水浴相比,该工艺高效、节能,产品性能优异,在聚羧酸减水剂掺量0.5%条件下,水泥净浆流动度达275 mm,砂浆减水率32.5%,且前期具有缓凝作用,后期对胶砂抗压强度增强显著,具有良好的工业应用前景。     

Synthesis of a bio-based plasticizer from vanillic acid and its effects on poly(vinyl chloride)

A new bio-based plasticizer, VA8-8, was prepared derived from vanillic acid, and its structure was verified by nuclear magnetic resonance. It was incorporated into poly(vinyl chloride) (PVC) to replace dioctyl phthalate (DOP), and its plasticizing performance was evaluated. The results indicated that VA8-8 shows good compatible with PVC resin, and has a excellent plasticizing effect for PVC. When DOP was partially or completely substituted with VA8-8, the T_g value PVC blends dropped from 34.6 to 24.3°C and the elongation at break increased from 196.4% to 301.9%, suggesting the enhanced plasticizing efficiency of plasticizer. The plasticizing mechanism was also simulated, and the interactions between VA8-8 and PVC molecules were discussed. The thermogravimetric analysis showed VA8-8 can more effectively improve the thermal stability of PVC than DOP. In addition, the migration resistance of VA8-8 was generally superior to that of DOP. Therefore, VA8-8 is a comparable to or better plasticizer than DOP, and it is a promising alternative plasticizer for PVC.     

Effect of auxiliary blowing agents on properties of rigid polyurethane foams based on liquefied products from peanut shell

The bio‐based rigid polyurethane (PU) foams were successfully prepared based on liquefied products from peanut shell with water as the blowing agent. The influence of reaction parameters on properties of rigid PU foams was investigated. Rigid PU foams showed excellent compressive strength and low shrinkage ratio, whereas their open‐cell ratio and water absorption were higher. Therefore, rigid PU foams were synthesized with petroleum ether, diethyl ether, and acetone as auxiliary blowing agents and their inner temperature, shrinkage performance, density, compressive strength, water absorption, and open‐cell ratio were determined. The results indicated that above rigid PU foams showed lower compressive strength than the original foam but their water absorption and close‐cell ratio were improved. Compared with the original foam, the highest inner temperature of rigid PU foams with petroleum ether, diethyl ether, and acetone as auxiliary blowing agents was reduced by 11, 19, and 23 °C, respectively. Typically, foams with petroleum ether as auxiliary blowing agent displayed better water absorption and swelling ratio in water and exhibited obvious improvement in close‐cell ratio. These foams were preferable for application in thermal insulation materials because of low thermal conductivity and better corrosion resistance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45582.     

Preparation and curing behavior of latent 2-PhIm-PS microcapsule curing agent for epoxy resin

A core–shell microcapsule latent epoxy curing agent (2-PhIm-PS) is obtained by solvent evaporation method with 2-phenyl imidazole (2-PhIm) as the core material and polystyrene (PS) as the wall material. The microcapsule parameters, morphology, structure, curing behavior, and the mechanic properties of cured epoxy resin with this microcapsule latent curing agent were characterized through comparing with 2-PhIm. The particle size distribution of the microcapsule is narrow, the average particle size is about 10.56 μm, and the core material content is 23%. The prepared 2-PhIm-PS microcapsule curing agent has excellent latent curing properties. It can completely cure epoxy resin E-51 within 10 min at 130°C, and its latent period can be more than 40 days at room temperature. In addition, the curing kinetics of one-component epoxy resin curing system (E-51/2-PhIm-PS) composed of 2-PhIm-PS microcapsules and epoxy resin E-51 is also studied by using Kissinger equation, Flynn–Wall–Ozawa and Crane formula. The results provide an outline for the evaluation on the applicability of the microcapsule curing agent of 2-PhIm-PS for epoxy resin.     

Effect of storage time on the characteristics of a waterborne polyurethane/tetraethoxysilane mixture and the properties of prepared films

Waterborne polyurethane (WPU) is one of the most important resins. The properties of WPU can be modified by introducing inorganic components. Tetraethoxysilane (TEOS) is a precursor for preparing inorganic polymers and can be used to prepare WPU/silica hybrids. In this study, WPU dispersion was synthesized by reacting polytetramethylene ether glycol and dimethylolpropionic acid with isophorone diisocyanate, followed by chain extension with ethylenediamine. After mixing WPU with TEOS, the mixture was sealed and stored at room temperature for different lengths of times. The influence of time on the characteristics of the WPU/TEOS mixture and the properties of films were investigated. The results showed that the viscosity, surface tension and average particle size of the mixture increased with prolonged storage time. ²⁹Si-NMR analysis indicated that the structure of silica exists in the WPU film. DSC, DMA and TGA results showed that WPU/silica films made from the mixture have less thermal activity, higher storage modulus, lower damping peak heights and better heat resistance after relatively long storage times.     

Synthesis of a novolac‐based 3‐aminopropylsiloxane resin and its application for the removal of Cu2+, Cr3+, and Ni2+ from electroplating wastewater

Novolac resin was modified with 3‐aminopropyltrimthoxysilane to obtain phenol‐formaldehyde‐aminopropylsiloxane resin (PF‐APS). Fourier transformation infra‐red spectra, thermogravimetric analysis, elemental analysis, and pH‐metric titration were used to characterize PF‐APS. Its chemical formula was suggested to be C₁₄H_12.49N_0.1O₂Si_0.1. The resin shows high experimental metal ions uptake capacity within short time of equilibration. The metal capacity was determined by atomic absorption spectrometry to be 0.787 mEq Cu/g. Maximum separation efficiencies of Cu²⁺, Cr³⁺, and Ni²⁺ from aqueous solutions on PF‐APS were at pH 8.0 and time of stirring 60 min; 94.0%, 90.8%, 83.2%, respectively. No significant interference from the background ions Na⁺, Cl^?, and was observed on the separation process. The heavy metal ions were eluted using 0.01 mol L^?1 EDTA at 65°C releasing >94% of the separated metal ions. The method of separation was applied successfully to remove the heavy metal ions Cu²⁺, Cr³⁺, and Ni²⁺ from electroplating wastewater from Dekirnis, Dakahlia Governorate, Egypt. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40993.     

Synthesis of solvatochromic merocyanine dyes and their immobilization to polymers

Solvatochromic merocyanine dyes were immobilized onto polymer surfaces and copolymerized with acrylic resins, yielding novel reversibly solvatochromic polymers, which were used as solvent polarity indicators that exhibited different colors in water and alcohols. To generate solvatochromic polymer for solvent polarity indication, two solvatochromic merocyanine dyes containing moieties, which allow their immobilization onto polymer surfaces, or copolymerization with acrylic and vinyl monomers, were sequentially synthesized in four and six steps. Merocyanine dye (E)‐2‐(2‐(1‐(6‐aminohexyl)pyridinium‐4‐yl)vinyl)‐4,6‐dichlorophenolate (AHPVD) was prepared with a terminal aminohexyl group which allowed covalent bonding to activated carboxylated or sulfonated polymeric materials. The dyes were covalently bonded to the polymer surfaces, such as, nylon, polycarbonate, polyethylene terephthalate, and silicone. Solvatochromic merocyanine dye (E)‐2‐(2‐(1‐(6‐acrylamidohexyl)pyridinium‐4‐yl)vinyl)‐4,6‐dichlorophenolate (AAPVD) was synthesized for radical copolymerization with acrylate and vinyl monomers and oligomers. Side‐chain solvatochromic merocyanine‐containing hydrophilic polymers with differential water and alcohol absorption were obtained upon photoinitiated radical copolymerization with specially formulated acrylated resins. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44451.     

Synthesis and performance of a modified polycarboxylate dispersant for concrete possessing enhanced cement compatibility

It is well established that the performance of polycarboxylate (PCE) superplasticizers can be severely affected by the composition of individual cements. Here, a novel allylether/maleic anhydride (APEG)‐based PCE was synthesized using allyl maleate monomer as a new, additional building block. When polymerized into the PCE main chain, this building block was found to form a cyclic lactone structure. The resulting PCE molecule was tested with respect to the dispersing force in cements possessing different phase compositions and alkali sulfate (K₂SO₄) contents. These data were compared with those from conventional APEG‐ and methacrylate ester (MPEG)‐type PCEs. Results obtained from cement paste flowability and adsorption measurements suggest that the modified PCE disperses all cement samples well and hence is more robust against variations in cement composition. Apparently, the new building block induces a higher affinity of the polymer to the surface of cement and can form a denser polymer layer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of a perfluorooctanoic acid molecularly imprinted polymer for the selective removal of perfluorooctanoic acid in an aqueous environment

Perfluorooctanoic acid (PFOA) contamination in the environment is a global problem. The aqueous phase is the main medium for PFOA because of its moderate solubility. Adsorption is a feasible way to remove PFOA because of its chemical and biological stability. In this study, a new type of molecularly imprinted polymer (MIP) for the selective adsorption of PFOA in aqueous solutions was synthesized by the precipitation polymerization method with PFOA as the template molecule after optimization. The adsorption kinetics and isotherms of the MIP adsorbent toward PFOA were studied, and the effects of the pH and cations on the adsorption were investigated with batch experiments. The results show that acrylamide (AAM) was the best functional monomer, and the optimal molar ratio of PFOA to AAM to ethylene glycol dimethacrylate (crosslinker) was 1:6:25. The optimized MIP adsorbent had a high affinity for PFOA, and the uptake percentage by the MIP adsorbent was 1.3–2.5 times that of the nonimprinted polymer (NIP) when PFOA existed alone. A maximum PFOA sorption capacity of 5.45 mg/g based on the Langmuir isotherm model was achieved with the MIP adsorbent. The MIP adsorbent exhibited a high selectivity for PFOA over competitive compounds (other perfluorinated alkyl carboxylic and sulfonic acids), whereas the NIP did not. Approximately 90% of the PFOA in the mixture was removed by the MIP adsorbent; this was 18 times that of the NIP. Moreover, the regenerability of the MIP adsorbent was confirmed in five sequential adsorption–desorption cycles without a significant reduction in the PFOA uptake. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43192.     

Influence of the addition of PEG into PCL-based waterborne polyurethane-urea dispersions and films properties

In this work, segmented waterborne polyurethane-urea (WBPUU) dispersions containing hydrophobic polycaprolactone (PCL) and hydrophilic poly(ethylene glycol) (PEG) in different molar ratios are synthesized and used for the subsequent preparation of films by casting. The molar ratio of PEG is gradually increased up to 0.20 in order to analyze the effect of low hydrophilic PEG content (from 1.7 to 7.1 wt %) on the properties of resulting dispersions and films. Regarding the dispersions, the addition of PEG results in an increase of the particle size, from 86 ± 1 in the case of pure PCL-based system to 112 ± 15 for systems containing 7.1 wt % of PEG, as well as in the formation of a core–shell structure in the particles. Films show different behaviors depending on their PEG content. WBPUUs containing just PCL or very low content of PEG in the soft segment present higher stiffness. However, the addition of PEG in a content of 3.4 wt % or higher hinder the ability of the short-range ordering of the hard segment, increasing the elongation at break from 842 ± 102 MPa for PCL-based WBPUU to 1312 ± 84 MPa for the system with the highest PEG content. Systems with higher PEG content form nanoparticles with more segregated core–shell structures inducing to the film a higher hydrophilicity. Hence, the addition of PEG to a PCL-based WBPUU allows to tune the properties of the resulting film increasing the range of application of these materials. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48847.     

Kinetic study on free radical grafting of polyethylene with acrylic acid by reactive extrusion

In the reactive extrusion process for the free radical grafting of acid monomers onto polyethylene, monomer grafting and homopolymerization occur simultaneously and interact with each other. Using an incremental theory, mathematical models of conversions for monomer grafting and homopolymerization were separately constructed to predict the grafting degree, mass of homopolymer and grafting efficiency. Effects of the barrel temperature, initial monomer and initiator concentrations on grafting behaviors were investigated. The barrel temperature and initial monomer concentration were shown to be the main process parameters for controlling the grafting degree. The grafting degree and mass of homopolymer increased significantly with increasing barrel temperature and monomer concentration and increased marginally with increasing initiator concentration. No significant improvement in the grafting efficiency was observed. The predictions of the models are in good agreement with experimental data. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40990.     

Preparation of amphoteric polycarboxylate superplasticizers and their performances in cementitious system

A series of amphoteric polycarboxylate (PC) polymers were synthesized by radical copolymerization of acrylic acid (AA), [3‐(methacryloylamino) propyl] trimethylammonium chloride (MAPTAC) and ω‐methoxypolyoxyethylene methacrylate ester (MPEGMA). Cationic groups were introduced in to PC molecules with expectation of less retardation effect on cement hydration compared to the traditional anionic PC superplasticizers. The content of cationic groups in polymer was varied by changing the monomer ratio of MAPTAC to AA in the synthesis recipes. The structure of the synthesized amphoteric PCs was verified by gel permeation chromatography (GPC) and Fourier transform infrared spectroscopy (FTIR). The performances of the amphoteric PCs were evaluated by measurement of flowability and zeta‐potential of cement pastes and adsorption amount of PC in cement pastes. Impacts of the PCs on cement hydration were studied by isothermal calorimetry. It is concluded that both anionic and cationic PC polymers can be effectively adsorbed onto the surface of cement particles and thus change the zeta potential of cement pastes. The adsorption amounts of the amphoteric PCs decrease with increasing content of cationic units. A proper incorporation of cationic units into PC polymers may lead to a higher fluidizing performance in fresh cement pastes. The amphoteric PC polymers with higher content of cationic units show less retardation effect on cement hydration and hence higher early strength of cementitious materials may be achieved by using amphoteric PCs with appropriated content of cationic units without losing their plasticizing efficiency. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41348.     

The effect of component addition order on the properties of epoxy resin/polyurethane resin interpenetrating polymer network structure

Epoxy resin (ER) is one of the most important synthetic resins, but it has the disadvantage of lacking impact resistance. However, it can be improved by mixing with polyurethane resin (PU). In this study, Epon 828, triethylenetetramine (TETA), polytetramethylene ether glycol (PTMG), isophorone diisocyanate (IPDI), and dibutyltin dilaurate (DBTDL) were used as raw materials to prepare ER/PU interpenetrating polymer network structures (IPNs) by three different blending processes. The results showed the reactivity between TETA and IPDI were greater than that between TETA and ER. When ER/TETA/PTMG/IPDI/DBTDL were mixed at the same time, or ER and PU resins were prepared separately and then mixed, the ER/PU composites produced had a phase separation inside the structure. The most appropriate blending method was to mix ER with PTMG, IPDI, DBTDL first, and then add TETA after 10 min. The composite formed had a uniform appearance, and had better physical, mechanical, and thermal properties than the others did.