马来酸酐聚羧酸减水剂的合成、表征与缓释机理

聚羧酸减水剂（PC）是现代高性能混凝土不可或缺的组分,本文以马来酸酐（MAH）、丙烯酸（AA）、甲基烯丙基聚氧乙烯醚（TPEG）为单体,采用水溶液自由聚合的方法合成马来酸酐聚羧酸减水剂（MAHPC）;实验通过IR及GPC对减水剂分子进行相应的结构性能表征,明确了MAHPC的分子结构为带有长侧链的梳状结构。实验结果表明：随着MAH对AA替代量的增加,MAHPC分子中的COO–浓度减小,从而在水泥颗粒表面的吸附量减小,对水泥浆体的分散性能减弱;MAHPC对水泥浆体具有较好的缓释性,经过3h流动度损失后,水泥浆体仍有良好的工作性;MAHPC分子中的COO–浓度对水泥浆体的流动度有直接影响,在碱性环境的水泥浆体中,MAHPC中的酸酐键水解生成COO–,COO–作为锚固基团,吸附于显示正电性的水泥颗粒及水泥水化物上,发挥其烷氧基长侧链的空间位阻和静电斥力效应,两者协同达到分散水泥颗粒的作用。     

Regulating the arm structure of star‐shaped polycarboxylate superplasticizers as a means to enhance cement paste workability

Star‐shaped superplasticizers, which incorporated polyol ester with unsaturated bond at their cores and bore comb‐type structures as their arms were synthesized via esterification‐copolymerization in aqueous phase from pentaerythritol, acrylic acid (AA), and isopentenyl oxy poly(ethylene glycol ether) (TPEG). The monomer ratios of AA and TPEG were varied and comonomer sodium methallyl sulfonate (SMAS) bearing short side chains was added to regulate the arm structure of star‐shaped polycarboxylate superplasticizers (SPCEs). The effects of the SPCEs on cement paste were investigated and the cement dispersion as well as early hydration mechanism were explored. As a main result, SPCEs with SMAS and certain molar ratios for anchoring groups and PEO side‐chains in their arm structure exhibited good paste dispersion and fluidity retention, which also delayed the early hydration process and prolonged both the initial and the final setting time. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46312.     

Low‐temperature photopolymerization and post‐cure characteristics of acrylates

Near‐infrared spectroscopy was used to investigate the post‐cure characteristics of acrylates polymerized from ? 75 °C up to room temperature. The results obtained showed that the double bond conversion increased with increasing initiator concentration. Post‐cure was much more striking for samples cured at lower temperatures. The chemical structure of monomer and photoinitiator had a great effect on the post‐cure process. The greater the functionality, the lower the final double bond conversion and the more distinct the post‐cure effect. Copyright © 2006 Society of Chemical Industry Society of Chemical Industry     

β-环糊精侧链对聚羧酸减水剂抑制蒙脱土的影响

采用水泥净浆和混凝土试验,详细研究了β-环糊精侧链对聚羧酸减水剂抑制蒙脱土负效应的影响。试验表明,与仅含有聚氧乙烯侧链的传统聚羧酸减水剂相比,蒙脱土对掺加含有β-环糊精侧链的聚羧酸减水剂水泥净浆流动度的负作用影响明显减弱;蒙脱土（1.0%,以砂质量计）存在时,为获得与无蒙脱土时相同的混凝土坍落度,β-环糊精类聚羧酸减水剂的掺量增幅减小,掺加β-环糊精类聚羧酸减水剂的混凝土抗压强度下降幅度减小。结合吸附试验分析,β-环糊精类聚羧酸减水剂抑制蒙脱土负效应能力的增强应归功于其侧链中的β-环糊精基团,β-环糊精基团具有中空筒状的刚性结构,其显著的空间位阻效应将阻止蒙脱土颗粒继续吸附其他β-环糊精类聚羧酸分子,进而提高聚羧酸减水剂抑制蒙脱土负效应的能力。     

Temperature of post‐flashover compartment fires—Calculations and validation

This paper describes and validates by comparisons with tests a one‐zone model for computing temperature of fully developed compartment fires. Like other similar models, the model is based on an analysis of the energy and mass balance assuming combustion being limited by the availability of oxygen, ie, a ventilation‐controlled compartment fire. However, the mathematical solution techniques in this model have been altered. To this end, a maximum fire temperature has been defined depending on combustion efficiency and opening heights only. This temperature together with well‐defined fire compartment parameters was then used as a fictitious thermal boundary condition of the surrounding structure. The temperature of that structure could then be calculated with various numerical and analytical methods as a matter of choice, and the fire temperature could be identified as a weighted average between the maximum fire temperature and the calculated surface temperature of the surrounding structure as a function of time. It is demonstrated that the model can be used to predict fire temperatures in compartments with boundaries of semi‐infinitely thick structures as well as with boundaries of insulated and noninsulated steel sheets where the entire heat capacity of the surrounding structure is assumed to be concentrated to the steel core. With these assumptions, fire temperatures could be calculated with spreadsheet calculation methods. For more advanced problems, a general finite element solid temperature calculation code was used to calculate the temperature in the boundary structure. With this code, it is possible to analyze surrounding structures of various kinds, for example, structures comprising several materials with properties varying with temperature as well as voids. The validation experiments were accurately defined and surveyed. In all the tests, a propane diffusion burner was used as the only fire source. Temperatures were measured with thermocouples and plate thermometers at several positions.     

Synthesis and post‐polymerization modification of maleimide‐containing polymers by ‘thiol‐ene’ click and Diels–Alder chemistries

This mini‐review provides an introduction to the key work in the area of synthesis and post‐polymerization functionalization of maleimide‐functional polymers. The versatility and utility of the maleimide group in the efficient functionalization of polymers by both ‘thiol‐ene’ Michael addition and Diels–Alder cycloaddition chemistries are highlighted. Copyright © 2011 Society of Chemical Industry     

Collection efficiencies of various designs of post‐cyclone

Post‐cyclone (PoC) is a novel secondary dust separator, which collects a certain fraction of the particles escaping through the vortex finder of a reverse flow cyclone. Due to the residual swirl in the vortex finder, the particles in the effluent air are concentrated at the wall of the vortex finder in an outer annulus. The particles in the outer annulus are split from the main stream and collected in a bleed flow. This paper presents the experimentally determined collection efficiencies of various designs of PoC. Depending on the design, operating conditions and the size and density of the particles, PoC can reduce the emission of the parent cyclones by 5% to 50%. In some experiments, the bleed flow from PoC is recycled back to the inlet of the cyclone. Significant improvement in the removal of fines occurs when the bleed flow is recycled to the inlet.     

Modeling of circulating fluidized beds systems for post‐combustion CO2 capture via temperature swing adsorption

The technology of circulating fluidized beds (CFBs) is applied to temperature swing adsorption (TSA) processes for post‐combustion CO₂ capture employing a commercial zeolite sorbent. Steady state operation is simulated through a one‐dimensional model, which combines binary adsorption with the CFB dynamics. Both single step and multi‐step arrangements are investigated. Extensive sensitivity analyses are performed varying the operating conditions, in order to assess the influence of the main operational parameters. The results reveal a neat superiority of multi‐step configurations over the standard one, in terms of both separation performance and efficiency. Compared to fixed‐bed TSA systems, CFB TSA features a high compactness degree. However, product purity levels are limited compared to the best performing fixed‐bed processes, and heat management within the system appears to be a major issue. As regards energy efficiency, CFB systems place themselves in between the most established absorption‐based technologies and the fixed‐bed TSA. © 2017 The Authors AIChE Journal published by Wiley Periodicals, Inc. on behalf of American Institute of Chemical Engineers AIChE J, 64: 1744–1759, 2018     

Influence of polymer microstructure on the performance of post‐treated latex‐based pressure sensitive adhesives

Latex‐based butyl acrylate (BA)/acrylic acid (AA)/2‐hydroxyethyl methacrylate (HEMA) pressure sensitive adhesive (PSA) films with various microstructures were heated to improve their performance. The treated PSA films showed significantly better performance than original latex‐based PSA films with similar polymer microstructures. The effect of the heat treatment depended on the polymer microstructure of the untreated PSA films (or corresponding latices). Decreasing the amount of very small sol polymers (i.e., M_x < 2M_e) in gel‐free untreated PSA films, or both very small (i.e., M_x < 2M_e) and very large sol polymers (i.e., M_x > 20M_e) in gel‐containing untreated PSA films led to treated PSA films with significantly better performance. (Note: M_e is the molecular weight between two adjacent entanglement points in a polymer material.) In addition, simultaneously increasing the sol polymer molecular weight (M_w) as well as the size of the chain segments between two adjacent cross‐linking points (M_c) of the gel polymer in the original PSAs resulted in treated PSA films with better performance. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Cationic electron‐beam curing of a high‐functionality epoxy: effect of post‐curing on glass transition and conversion

This paper reports on the cationic electron‐beam curing of a high‐functionality SU8 epoxy resin, which is extensively used as a UV‐curing negative photoresist for micro‐electronics machine systems (MEMS) applications. Results show that elevated post‐curing treatment significantly increased both the conversion and the glass transition. The degree of conversion and the glass transition temperature were measured by using Fourier‐transform infrared (FTIR) spectroscopy and modulated differential scanning calorimetry (MDSC^®), respectively. The glass transition temperature (T_g), which has been observed to be dependent on the degree of conversion, reaches a maximum of 162 °C at 50 Mrad and post‐curing at 90 °C. The degradation pattern of the cured resin does not show much variation for exposure at 5 Mrad, but does show significant variation for 50 Mrad exposure at various post‐curing temperatures. A degree of conversion of more than 0.8 was achieved at a dosage of 30 Mrad with post curing at 80 °C, for the epoxy resin with an average functionality of 8 a feature simply not achievable when using UV‐curing. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of side‐chain polyimides for second‐order nonlinear optics via a post‐azo‐coupling reaction

A two‐step, generally applicable synthetic approach for nonlinear optical (NLO) side‐chain polyimides was developed. This included the preparation of a preimidized, organosoluble polyimide with benzene moiety pendant from main chains, followed by the covalent bonding of the NLO chromophores onto the polyimide backbone via a post‐azo‐coupling reaction. The degree of functionalization of polyimides was estimated by UV‐VIS spectroscopy. The glass transition temperature (T_g) of a polyimide decreased by only 10–20°C after the functionalization, which was much smaller than the decrease in T_g when the chromophores were chemically bonded to the polyimide main chains through an ether linkage using a post‐Mitsunobu condensation. The solubility and thermal stability of polyimides were also studied. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 290–295, 2000     

CO2 capture efficiency in post‐combustion using MWNT‐PAA in a packed bed column

The adsorption capacity of polyaspartamide (PAA) and multi‐wall carbon nanotubes with polyaspartamide (MWNT‐PAA) was investigated through a packed bed column with the flowing of flue gas composed of 15 % CO₂, 5 % O₂ and the balance N₂. The adsorption performed at 25 °C, 110 kPa and inlet gas flow rate of 60 mL/min resulted in high CO₂ adsorption capacity of 5.70 and 10.20 mmol‐CO₂/g for PAA and MWNT‐PAA, respectively. The adsorption kinetics was very high, so 7 min were enough for the effluent gas to reach the breakthrough after saturation. The consistency of adsorbents in recurring regeneration was successful through a continuous TSA system of 10 cycle adsorption‐desorption with temperatures of 25–100 °C. The evaluation of heat through differential scanning calorimetry (DSC) resulted in exothermic adsorption with heat release of 45.14 kJ/mol and 124.38 kJ/mol for PAA and MWNT‐PAA, respectively. The heat release was found favourable to promote the desorption as the temperature could rise after adsorption. This is an advantage for energy efficiency, as it depicts the potential of energy recovery. Thus, both adsorbent PAA and MWNT‐PAA were demonstrated to be promising for CO₂ adsorption capture in post‐combustion.     

Investigation of the clay sensitivity and cement hydration process of modified HPEG‐type polycarboxylate superplasticizers

In this work, three kinds of HPEG‐type polycarboxylate superplasticizers (PCs) were synthesized with three kinds of typical functional monomers: [diallyl dimethyl ammonium chloride (DMDAAC), 2‐hydroxyethyl methacrylate (HEMA), and 2‐(dimethylamino) ethyl methacrylate (DMAM), respectively. The effects of montmorillonite clay on the fluidity of cement/PC pastes were investigated. It was found that the fluidity was negatively affected by the clays in the order: DMAM‐PC < HEMA‐PC < conventional PC (CPC) < DMDAAC‐PC. The DMAM‐PC was found to disperse cement well even in presence of montmorillonite clay. The dispersion performance of DMDAAC‐PC was much more effectively affected by clay due to the reaction between ammonium and montmorillonite. More study including mortar fluidity, adsorption behavior and morphology of the cement samples were investigated in details. Thermogravimetric analysis and X‐ray diffraction experiments allowed us to observe the influence of PCs on the hydrated products. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46572.     

Green composites of organic materials and recycled post‐consumer polyethylene

Addition of organic fillers to post‐consumer recycled plastics can give rise to several advantages. First of all, the cost of these fillers is usually very low, the organic fillers are biodegradable contributing to an improved environmental impact and, last but not least, some mechanical and thermomechanical properties can be enhanced. Organic fillers are not widely used in the plastic industry although their use is increasing. Bad dispersion into the polymer matrix at high‐level content and poor adhesion with the matrix are the more important obstacles to this approach. In this work various organic fillers have been used with a post‐consumer plastic material originating from films for greenhouses. The properties of these green composites have been compared with those of materials filled with a conventional inorganic filler. The organic fillers cause slightly worse processability, due to an increase of viscosity, an enhancement of the rigidity and of the thermomechanical resistance similar to that measured for the inorganic filler, while a reduction of the impact strength is observed. Copyright © 2004 Society of Chemical Industry     

Synthesis of high metal‐complexation linear elastomers containing sym‐1,2,4,5‐tetrazine rings

We report the synthesis of polyurethane‐urea elastomers containing 1,2,4,5‐tetrazine covalently reacted within the main chains of the polymers. Our study investigates the synthesis of 3,6‐diamino‐1,2,4,5‐tetrazine (DAT), the polymerization reaction conditions for reacting DAT into the backbone of segmented polyurethane elastomers, and the metal‐complexation capabilities of tetrazine‐containing elastomers with cobalt (II) chloride. Tetrazines are highly colored and electro‐active heterocyclic moieties, which have a very high electron affinity which make them reducible at high to very high potentials. Upon complexation with metals, we observed a strong color shift of the polymers from deep red to blue indicating the binding efficacy for the polymers. We quantified the metal‐complexation capability of the tetrazine elastomers and determined a molar ratio of approximately two metal atoms per tetrazine allowing us to provide a plausible complexation mechanism for the active polymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of novel fluoroalkyl end‐capped oligomers containing phosphorus segments

New fluoroalkyl end‐capped oligomers containing pendant phosphoric acid groups wereprepared by the reactions of the corresponding monomer with fluoroalkanoyl peroxides. It was demonstrated that not only strong aggregations of fluoroalkyl segments but also hydrogen bonding could interact synergistically to form the highly viscoelastic fluids (gel‐like fluids) in aqueous solutions of these new fluoroalkyl end‐capped oligomers containing pendant phosphoric acid groups. Furthermore, these oligomers were able to reduce the surface tension of water effectively to exhibit a clear breakpoint resembling a CMC, and the modified stainless‐steel surface treated with these oligomers was shown to possess an excellent property imparted by fluorine. More interestingly, these oligomers were found to be potent and selective inhibitors against HIV‐1 replication in vitro. New fluoroalkyl end‐capped phosphonic acid and phosphonate oligomers were also prepared by the reactions of the corresponding phosphonic acid and phosphonate monomers, respectively, by the use of fluoroalkanoyl peroxides. These new fluoroalkyl end‐capped phosphonic acid and phosphonate oligomers were found to have a higher solubility in not only water but also in common organic solvents than that of the corresponding fluorinated oligomers containing pendant phosphoric acid groups, and these new oligomers were able to reduce the surface tension of these solvents quite effectively. Thus, these oligomers are expected to develop as new fluorinated oligosurfactants. Moreover, the modified poly(methyl methacrylate) surface treated with these phosphonate oligomers was clarified to exhibit a good oil‐repellency imparted by fluorine. In addition, fluoroalkyl end‐capped phosphonate homo‐ and cooligomers were found to form monomolecular films at the air–water interface. Therefore, these fluorinated oligomers are suggested to have high potential for new functional materials through not only their excellent properties imparted by both fluorine and phosphorus, but also through their biological properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 228–245, 2001     

Controlled release of carboxylic‐containing herbicides by starch‐g‐poly(butyl acrylate)

The use of starch‐g‐poly(butyl acrylate) as a new material for encapsulating carboxylic‐containing herbicides such as 2,4‐dichlorophenoxyacetic acid and 2,4,5‐trichlorophenoxyacetic acid for controlled release was studied. The herbicides were individually encapsulated within the modified starch substrate, which was graft‐copolymerized with a small amount of butyl acrylate. The modification of starch induced a hydrophobic behavior in the matrix, made it swell less, and caused the release rate to slow, especially for herbicides with higher water solubility. Therefore, the survival life of the starch products for controlled release could be expected to extend to some extent compared with that of natural starch. In addition, the effects of the molecular weight, herbicide content, and particle size on the swellability and release behavior were also investigated. Scanning electron microscopy revealed that the herbicides encapsulated within the starch matrix were dispersed in the form of tiny cell. Consequently, the herbicides encapsulated were released through diffusion. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1535–1543, 2001