Synthesis of zinc-containing epoxy resin

Novel epoxy resins containing zinc acrylate have been synthesized by reacting zinc acrylate with bisphenol-A and an excess of epichlorohydrin. Parameters such as epoxy equivalent weight, hydroxyl content, and hydrolyzable chlorine content have been estimated. These resins, characterized by IR, ¹H-NMR, and ¹³C-NMR, have been evaluated by thermal analysis. Curing was carried out with polyamide at 130°C for 24 h. Cured resins have improved thermal and chemical resistance. The reaction follows first-order kinetics with activation energy 86 and 34 kJ mol^?1 in the presence and absence of zinc acrylate. The role of zinc, which increases epoxidation due to formation of complex with bisphenol-A, has been discussed. © 1994 John Wiley & Sons, Inc.     

The mechanical and fatigue properties of flowable crosslink thermoplastic polymer blends based on self‐catalysis of transesterification

A flowable crosslink polymer blend was successfully developed through a reactive compounding process. An epoxy captained ethylene acrylate copolymer and a carboxylic acid and zinc ion contained ethylene acrylic copolymer were employed to react in a twin screw extruder to form a partially crosslink polymer blend which was flowable at high temperature due to the rapid transesterification catalyzed by the zinc ion in the polymer. The developed crosslink polymer blend showed a significant improvement of the mechanical strength, thermal stability, and fatigue performance compared to the neat ethylene acrylic copolymer because of the strong chemical crosslink among polymer chains. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44964.     

含金属离子丙烯酸共聚物的机械性能

合成了单官能度丙烯酸锌盐和单官能度甲基丙烯酸锌盐，并研究了其对丙烯酸共聚物机械性能的影响。结果表明，这两种锌盐都可以显著改善共聚物涂层的机械性能。     

不同交联剂对核壳型丙烯酸树脂乳液MFT及硬度的影响

采用半连续种子乳液聚合方法，以三羟甲基丙烷三丙烯酸酯（TMPTA）、N-羟甲基丙烯酰胺（NMA）、丙烯酸锌盐（ZA）为交联单体，合成了木器用交联型核壳丙烯酸树脂乳液，并借助差示扫描量热仪（DSC）、最低成膜温度（MFT）仪等测试手段考察了3种交联体系对树脂乳液MFT及硬度的影响。     

不饱和羧酸锌盐对NBR的增强

通过氧化锌与甲基丙烯酸或丙烯酸的中和反应,在丁腈橡胶（ＮＢＲ）生成了甲基丙烯酸锌或丙烯酸锌,研究了过氧化物硫化ＮＢＲ的力学性能和交联结构。结果表明,原位合成法甲基丙烯酸锌或丙焕酸锌增强ＮＢＲ可得到与直接加入法类似的增强效果,硫化胶具有高强度、高硬度和高伸长率;对交联结构的分析表明,硫化胶的良好性能与其含离子交联键有密切关系。     

Effect of lanthanide (La(III))‐containing ionomer on thermal stabilization of poly(vinyl chloride)

A type of lanthanide (La(III))‐containing ionomer based on acrylate processing aid (ACR) for poly (vinyl chloride) (PVC) was synthesized, and influence of the ionomer on thermal stabilization of PVC was investigated with visual color comparison and Congo red methods. Results revealed that the ionomer with a suitable La(III) content behaved as a good costabilizer to PVC. It was able to extend static stabilization time of PVC and postpone “zinc burning.” The stabilizing efficiency of the ionomer to PVC depended on ion content, which was discussed in terms of Eisenberg–Hird–Moore model. Moreover, Fourier transform infrared test verified that this ionomer can react with zinc stearate (ZnSt₂) to form some new structures, which is responsible for postponing “zinc burning.” The ionomer and epoxidized soybean oil exhibited a synergistic effect on the stabilizing efficiency of calcium stearate (CaSt₂)/ZnSt₂ stabilizer to PVC compounds. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mechanism of the copolymerization of styrene with methyl,ethyl, and n-butyl acrylates in the presence of zinc chloride

The complexes of methyl acrylate (MA), ethyl acrylate (EA) and n-butyl acrylate (BA) with zinc chloride (ZnCl₂) were prepared at 300 K and found to be polar in nature. The viscosity and density of the complexes increased while the tendency to form a binary complex decreased with increase in size of the alkyl substituents of the acrylate monomers. The copolymerization of MA and BA with styrene (Sty) followed a cross-propagation mechanism, whereas the copolymerization of EA with Sty followed a radical-complex mechanism in the presence of their complexes with ZnCl₂.     

Influence of intermolecular interactions on the melt rheology of a propylene–acrylic acid copolymer and its salts

Ionomers based on propylene–acrylic acid copolymer have been prepared and their rheological behavior studied. With different cations the melt viscosity at any shear rate increases as tributylamine salt < acid < zinc salt < sodium salt. Similarly, the activation energies for viscous flow follow the order polypropylene ～ tributylamine salt < acid ～ zinc salt < sodium salt. These results are a consequence of intermolecular interactions between salt groups for the metal acrylate derivatives and hydrogen bonding for the acid derivatives. Strong ionic interactions are absent in the tributylamine salt because of steric hindrance of the bulky amine substituents. The glass transition temperatures for these materials were equivalent. The elastic properties of these polymers follow a similar trend as does the viscosity.     

丙烯酸锌树脂的产业化及应用研究

介绍了无锡自抛光9188丙烯酸锌树脂的合成工艺和主要性能指标,以及以9188树脂为基料的无锡自抛光防污涂料的基础配方、性能检测及实船应用情况等。     

Synthesis and photopolymerization of 2‐(acryloyloxy)ethyl piperidine‐1‐carboxylate and 2‐(acryloyloxy)ethyl morpholone‐4‐carboxylate

Two low‐viscosity monomers, 2‐(acryloyloxy)ethyl piperidine‐1‐carboxylate (AEPC II) and 2‐(acryloyloxy)ethyl morpholone‐4‐carboxylate (AEMC), were synthesized with a non‐isocyanate route. The photopolymerization kinetics was monitored by real‐time infrared spectroscopy with a horizontal sample holder. The results indicated that AEPC II and AEMC had high ultraviolet curing rates and final double‐bond conversions, which could reach 90 and 95%, respectively. The glass‐transition temperatures of AEPC II/urethane acrylate resin (1/4 w/w), AEMC/urethane acrylate resin (1/4 w/w), and isobornyl acrylate/urethane acrylate resin (1/4 w/w) mixtures were 37.5, 45.6, and 57°C, respectively. The crosslink density of the AEMC/urethane acrylate resin (1/4 w/w) mixture was lower than that of the isobornyl acrylate/urethane acrylate resin (1/4 w/w) mixture. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Studies on corrosion resistant properties of sacrificial primed IPN coating systems in comparison with epoxy–PU systems

The continuous development in the field of protective coatings and the search for newer materials with improved properties have led to the emergence of interpenetrating polymer networks (IPNs) as binders for high performance organic coatings for corrosion protection. In this study, one such ambient curing IPN polymer alloy poly(epoxy–urethane–acrylate) developed specially for use in protective coatings has been studied. Undercoat and a topcoat based on the alloy have been formulated and coated over zinc ethyl silicate primed steel surfaces. Similar formulations based on an epoxy polyamide undercoat and a PU topcoat has been formulated and coated over zinc ethyl silicate primed steel surfaces. Both the systems were evaluated for their physical and corrosion resistant properties by subjecting them to accelerated laboratory tests and field test at a corrosive location. The results are reported and conclusions drawn in this paper.     

Cellulose graft copolymers. I. Graft copolymerization of ethyl acrylate with γ-irradiated cellulose from methanol–water systems

Ethyl acrylate was graft-copolymerized with γ-irradiated, purified cotton cellulose from methanol–water systems. The accessibility of the free radicals in the irradiated cellulose to water, methanol, ethyl acrylate, and methanol–water solutions was determined by electron spin resonance spectroscopy. The maximum scavenging of the radicals was recorded with the irradiated cellulose was immersed in methanol–water solution which had a composition of 50/50 vol-%. When ethyl acrylate was added to methanol–water solution (50/50 vol-%), maximum grafting on the irradiated cellulose occurred at a concentration of ethyl acrylate of about 20 vol-%. As the concentration of ethyl acrylate was decreased, maximum grafting occurred in solutions containing less than 50 vol-% methanol. It was also noted that maximum grafting of ethyl acrylate in methanol–water solutions to irradiated cellulose occurred at boundry conditions, that is, conditions where the ternary mixture was still one phase, slightly different from compositions which caused the mixture to separate into two phases. From methanol solution, maximum grafting occurred at a concentration of ethyl acrylate of 80 vol-%. The extent of grafting from methanol was less that obtained from methanol–water solutions at lower concentrations of ethyl acrylate. The accelerative effects of water was considered to be due to the Trommsdorff effect.     

Effects of monomer structure on the morphology of polymer network and the electro‐optical property of reverse‐mode polymer‐stabilized cholesteric texture

The morphologies of the polymer networks in the polymer network/LC composite of reverse‐mode polymer‐stabilized cholesteric texture (PSCT) films was observed. The polymer network/LC composite was prepared from photopolymerization of the acrylate monomers, which had rod‐like rigid cores in monomer/LC mixture. The effects of the structure of the acrylate monomers on the morphology of polymer network were studied. The acrylate monomer without flexible pacers between the acrylate functional groups and the rigid core formed rice‐grain‐like polymer network with poor orientation. The acrylate monomer with flexible pacers formed fiber‐like polymer network with better orientation. Meanwhile, the effects of morphology of polymer network on the electro‐optical property of reverse‐mode PSCT films were also investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel phosphinate-containing zinc polyacrylate and its utilization as flame retardant for polyamides

A new organophosphorus, zinc-containing polyacrylate is synthesized that has potential use as flame retardant for polyamides. To achieve this goal, the Phospha-Michael addition is utilized to selectively add 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO) to one acrylate group of zinc acrylate followed up by radical polymerization of the remaining acrylate group in a one-pot approach. To verify the effectiveness of the synthesis method, it is compared to a second two-step approach via diethyl zinc. In order to investigate the influence of molecular weight as well as phosphorus content on the flame retardant properties, the small-molecule complex zinc bis(3-(6-oxidodibenzo[c,e][1,2]oxaphosphinin-6-yl)propionate) and the nonphosphorus thermoset poly(zinc diacrylate) are synthesized as well. All three substances are investigated as flame retardants for pure and glass-fiber (GF) reinforced polyamide 6 (PA 6) and 66 (PA 66) in different compounds with and without melamine polyphosphate (MPP). Most of the samples show excessive dripping in the vertical burning test UL-94 V. However, V-1 classification is achieved in GF-reinforced PA 66 with the DOPO- and zinc-containing polyacrylate in combination with MPP. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47586.     

Postdecrystallization rates of grafted fibers and their effect on fiber elasticity. I. Effect of zinc chloride concentration

Rayon yarns grafted with poly(ethyl acrylate) become highly elastic following decrystallization in aqueous zinc chloride solutions. An increase in temperature speeds up the decrystallization rate but does not have a substantial effect on the ultimate elongation properties of the grafted fiber. Increasing the concentration of zinc chloride does not have a marked change in the extension properties of the grafted fiber until 70% zinc chloride. At this saturated concentration, there is a sudden and dramatic change in the elastic properties of the grafted fiber. In fact, the grafted fibers after decrystallization in 70% zinc chloride have elongations in excess of 800%.     

In situ preparation of zinc salts of unsaturated carboxylic acids to reinforce NBR

Through the neutralization reaction of zinc oxide (ZnO) and methacrylic acid (MAA) or acrylic acid (AA), zinc methacrylate (ZMA) or zinc acrylate (ZA) was in situ prepared in nitrile rubber (NBR). The mechanical properties and crosslinking structure of the resulting peroxide‐cured NBR vulcanizates were studied. The results showed that ZnO/MAA (AA) had a great reinforcing effect for NBR, and their amounts and ratio played important roles in influencing the mechanical properties. Such vulcanizate contains both covalent crosslinks and salt crosslinks, and the change in the tensile strength of the vulcanizate was related to the variation of the salt crosslink density. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2740–2748, 2000     

In Situ FT-IR Study of Diesel Hydrocarbon Oxidation Over Pt/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalyst

Abstract  

The catalytic performance of Pt/Al₂O₃ for the total oxidation of a hydrocarbon mixture of n-decane and 1-methylnaphthalene was investigated by using in situ FT-IR spectroscopy. Although carbonate and/or carboxylate species were mainly detected under steady-state conditions, the formation of an acrylate species during the initial stage of the reaction was observed under transient conditions. Based on a comparison of the reaction and formation behavior of the acrylate species and CO₂ as a gaseous product, it was proposed that the total oxidation of the hydrocarbon mixture proceeds via the formation of an acrylate species as a reaction intermediate.     

Pervaporation separation of 1,1,2‐trichloroethane–water mixture through crosslinked acrylate copolymer composite membranes

The separation of a chlorinated hydrocarbon from a dilute aqueous solution through a crosslinked acrylate copolymer–porous substrate composite membrane by pervaporation was investigated. Poly(n‐butyl acrylate‐co‐acrylic acid) and poly(n‐butyl acrylate‐co‐2‐hydroxyethyl acrylate) were synthesized and composite membranes were prepared, which were made from the crosslinked polymer and a porous substrate. Pervaporation measurement was carried out for a dilute aqueous solution of 1,1,2‐trichloroethane at 25°C and under a vacuum on the permeate side (below 10 mmHg). The separation factor, overall flux, 1,1,2‐trichloroethane concentration in the membrane, and the degree of swelling decreased with increase in the acrylic acid or 2‐hydroxyethyl acrylate content of the acrylate copolymer. The influence of the crosslinking agent content on the pervaporation performance was small, and the separation factor and the overall flux showed a convex curve. The structure of the crosslinking agent had no effect on the separation. The influence of the pore size of the substrate and the thickness of the polymer layer on the separation of 1,1,2‐trichloroethane was observed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 983–994, 1999     

纳米锌/硫化钠/环氧丙烯酸酯涂层的阻燃性能研究

为探讨纳米锌与硫化钠对环氧丙烯酸酯(EA)涂层的阻燃效果,以乙酸锌和苜蓿粉为原料,利用植物还原法制备了纳米锌,将其与硫化钠及EA配合,经紫外光固化制备纳米锌/硫化钠/EA阻燃涂层。通过红外、紫外、差示扫描量热仪及力学分析仪对其阻燃、透光率、热稳定性及硬度等性能进行测定。结果表明:当纳米锌质量分数为10%时,纳米锌/硫化钠/EA涂层阻燃性能最佳,涂层残余率达19.47 %,极限氧指数达31。所有涂层硬度均为6H,涂层热稳定性随纳米锌质量分数的增加而增加,而透光率逐渐下降。     

无氧化亚铜自抛光防污涂料的研制

制备了丙烯酸锌树脂,对无氧化亚铜自抛光防污涂料的配方及防污性能、电化学性能、配套性能等进行了研究工作,表明该无氧化亚铜自抛光防污涂料具有良好的防污性能、底面漆配套性能等。