In situ preparation of cyclohexanone formaldehyde resin/layered silicate nanocomposites

In this study, in situ modified cyclohexanone formaldehyde resin (CFR) was prepared from clay (montmorillonite) and polydimethylsiloxane with diamine chain ends [α,ω‐diamine poly(dimethyl siloxane) (DA.PDMS)] in the presence of a base catalyst. Different clay contents (from 0.5 to 3 wt %) were used to produce clay‐modified nanocomposite ketonic resins [layered clay (LC)–CFR] and clay‐ and DA.PDMS‐modified nanocomposite ketonic resins (DA.PDMS–LC–CFR). The polymeric nanocomposite material prepared by this method was directly synthesized in one step. These nanocomposites were confirmed from X‐ray diffraction to have a layered structure with a folded or penetrated CFR, and they were further characterized via Fourier transform infrared spectroscopy–attenuated total reflectance and NMR spectroscopy. The thermal properties of all of the resins were studied with differential scanning calorimetry and thermogravimetric analysis. All of the resins showed higher thermal stability than their precursor CFR resin. The obtained samples were also characterized morphologically by scanning electron microscopy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39918.     

Modified wheat gluten as a binder in particleboard made from reed

To evaluate the utilization of reed in environmental friendly high‐density particleboard, modified wheat gluten was used with urea‐formaldehyde as a binder in different ratios, applying the optimum conditions obtained on using UF resin alone. The scanning electron microscopy of the reed fibers showed that the fibers are cylindrical in shape, which helps in enhancing the adhesion between the binder and the inner and outer surfaces of the fibers. The dependence of the mechanical properties (modulus of rupture, modulus of elasticity and the internal bond) and the physical properties (water absorption and thickness swelling) on the urea‐formaldehyde/modified gluten ratios was studied. Addition of 1% and 2% boric acid as a fungicide to the binder mixture resulted in no significant change in the mechanical properties and slight improvement in the physical properties of the produced particleboard. Thermogravimetric analyses of selected samples were done to study the thermal stability of the particleboard bonded with the modified binder with and without boric acid. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis of cyclohexanone formaldehyde resin‐methylmethacrylate block‐graft copolymers via ATRP

Well defined block‐graft copolymers of cyclohexanone‐formaldehyde resin (CFR) and methylmethacrylate (MMA) were prepared via atom transfer radical polymerization (ATRP). In the first step, cyclohexanone formaldehyde resin (CFR) containing hydroxyl groups were modified with 2‐bromopropionyl bromide. Resulting multifunctional macroinitiator was used in the ATRP of MMA using copper bromide (CuBr) and N,N,N′,N″,N″‐pentamethyl‐diethylenetriamine (PMDETA) as catalyst system at 90°C. The chemical composition and structure of the copolymers were characterized by nuclear magnetic resonance (¹H‐NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and molecular weight measurement. Molecular weight distributions of the CFR graft copolymers were measured by gel permeation chromatography (GPC). M_n values up to 19,000 associated with narrow molecular weight distributions (polydispersity index (PDI) < 1.6) were obtained with conversions up to 49%. Coating properties of synthesized graft copolymers such as adhesion and gloss values were measured. They exhibited good adhesion properties on Plexiglas substrate. The thermal behaviors of all polymers were conducted using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

New melamine–formaldehyde–ketone resins. VI. Preparation of filled molding compositions and compression‐molding materials from reactive solvents based on cyclohexanone

The conditions and a method of preparing new molding compositions and filled compression‐molding materials from melamine–formaldehyde–cyclohexanone resins are described. The resins were obtained from melamine solutions in a reactive solvent prepared by the reaction of 1 mol of cyclohexanone with 7 mol of formaldehyde. The fillers were wood powder and sulfite cellulose. The thermal properties of the samples prepared from the compositions were studied with dynamic thermal analysis, thermogravimetry, and differential scanning calorimetry analysis. Selected mechanical properties [Brinell hardness, unnotched impact strength (Charpy method), and bending strength] of the cured resins were also measured. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polypyrrole–vinyl aniline modified cyclohexanone formaldehyde resin copolymers: a comparative study of the resin preparation

In this study, the synthesis of polypyrrole‐b‐vinyl aniline modified cyclohexanone formaldehyde resin (PPy‐b‐CFVAnR) block copolymers by a combination of condensation polymerization and chemical oxidative polymerization processes was examined. First, a cyclohexanone formaldehyde resin containing vinyl aniline units [4‐ vinyl aniline modified cycl?ohexanone formaldehyde resin (CFVAnR)] was prepared by a direct condensation reaction of 4‐vinyl aniline and cyclohexanone with formaldehyde in an in situ modification reaction. CFVAnR and pyrrole (Py) were then used with a conventional method of in situ chemical oxidative polymerization. The reactions were carried out with heat‐activated potassium persulfate salt in the presence of p‐toluene sulfonic acid in a dimethyl sulfoxide–water binary solvent system; this led to the formation of desired block copolymers. The effects of the oxidant–monomer molar ratio, dopant existence, addition order of the reactants, and reaction temperature on the yield, conductivity, and morphology of the resulting products were investigated. PPy‐b‐CFVAnR copolymers prepared with a resin‐to‐Py molar ratio of 1:40 showed conductivity in the range 3.7 × 10^?1 to 3.8 × 10^?2 S/cm. Oxidant‐to‐Py molar ratios of 0.5 and 1.0 were proposed to be the optimum stoichiometries for higher conductivity and yield, respectively, of the copolymer. The morphology of the copolymer (PPy‐b‐CFVAnR) was investigated with environmental scanning electron microscopy analyses. The results indicate that the surface of the copolymer was composed of well‐distributed nanospheres with average particle diameters of 60–85 nm. Also, the synthesized PPy‐b‐CFVAnR had a higher thermal stability than the pure CFVAnR. The chemical composition and structure of the PPy‐b‐CFVAnR copolymers were characterized by Fourier transform infrared spectroscopy and measurement. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42841.     

Replacing 100% of phenol in phenolic adhesive formulations with lignin

Lignin, produced as a byproduct of pulp and paper and bioethanol industries, is a polyphenolic compound that has excellent potential to be used as phenol replacement in phenolic adhesive formulation. In this study, the phenol portion of phenol formaldehyde (PF) resin has been replaced by an agricultural‐based lignin, which was produced as a byproduct of a cellulosic bioethanol process through dilute‐acid pretreatment and enzymatic hydrolysis from corn stover. The PF resol resin was formulated using isolated lignin under alkaline condition. Chemical, physical, and thermal properties of the isolated lignin, PF resin and adhesive were measured using advanced analytical techniques such as Fourier transformed infrared spectroscopy (FTIR), size exclusion chromatography (SEC), phosphorous nuclear magnetic resonance spectroscopy (³¹P NMR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The developed 100% lignin‐based adhesive and a commercially formulated phenol resorcinol formaldehyde (PRF, as reference) were used to prepare single‐lap‐joint samples for mechanical testing. The plywood samples were pressed under exactly the same conditions (time, temperature, and pressure) as what recommended for the commercial PRF formulation. According to two‐way ANOVA results, statistically there was no significant difference between the shear strengths of plywood samples made with 100% lignin‐based adhesive and those made with the commercial PRF resin. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45124.     

A study on composites from phenol‐formaldehyde‐casein resin

A modified phenol‐formaldehyde (PF) resin was synthesized under alkaline condition in varying proportion of casein up to 20% (w/w) of phenol. All the prepared resins were characterized by free phenol content, free formaldehyde content, viscosity measurements, number average molecular weight determination by conductometry and Infrared Spectroscopy (IR). Their curing kinetics was studied isothermally and by differential scanning calorimetry (DSC) on dynamic runs. The resin samples were cured using concentrated hydrochloric acid and hexamine individually. Cured resins were characterized by IR and Thermogravimetry (TGA). Glass fabric reinforced composites (GFRC) were fabricated by maintaining 40 : 60 proportion of resin to reinforcement material. The laminates thus formed were characterized for their mechanical properties and chemical resistance. Enhancements in thermal stability of the resin as well as toughness of composite with increase in casein content were observed for the resins studied. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Properties of poly(urea‐formaldheyde) microcapsules containing an epoxy resin

Physical properties of urea‐formaldehyde microcapsules containing an epoxy resin are presented and discussed. Microcapsules were prepared by in situ polymerization of monomers in an oil‐in‐water emulsion. Differential scanning calorimetry, thermogravimetric analysis, and scanning electronic microscopy were applied to investigate thermal and morphological microcapsule properties. Microencapsulation was detected by means of FTIR and Raman techniques. It was found that the amount of encapsulated epoxy resin as well as the extent of urea‐formaldehyde polymerization depends on the reaction temperature and the stirring speed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and properties of composites based on melamine‐formaldehyde foam and nano‐Fe3O4

In this work, a novel melamine‐formaldehyde‐Fe₃O₄ foam was prepared from a mixture containing melamine‐ethanolamine‐formaldehyde resin, melamine‐glycol‐formaldehyde resin and carboxylated Fe₃O₄ nanoparticles by microwave foaming method. The two resins were characterized by ¹³C‐NMR, respectively. The structures of foams, mechanical and fire‐retardant properties were experimentally characterized separately by scanning electron microscopy, universal testing machine, limit oxygen index, thermogravimetry‐differential thermal analysis, and Fourier transform infrared spectra. The effects of the resin viscosity, emulsifier, nucleating agent, curing agent, silicone oil, microwave heating time and blowing agent on the structure of foam were investigated. Results showed that the properties of foam were decided by not only the molecular structure but also structure of foam, and the carboxylated Fe₃O₄ nanoparticles can improve the toughness and flame retardant properties of magnetic foam obviously from both aspects. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2688–2697, 2013     

Nanoencapsulation mechanism of fragrant oil: effect of formaldehyde − melamine molar ratio

Encapsulation of essential oils by in situ polymerization is commonly used to contain the oil and thus ensure its controlled release. Melamine resin formaldehyde is one of the most widely used shell materials due to its thermal and chemical stability. One of the factors that influences the properties of the capsules is the molar relationship between monomers. The effect of formaldehyde ? melamine (F/M) molar ratios 3, 4 and 6 on the nanoencapsulation, morphology and properties of nanocapsules was investigated. The morphology and particle size were investigated by the scanning electron microscopy and atomic force microscopy techniques. The composition of the formaldehyde ? melamine resins was determined by Fourier transform infrared spectroscopy, and the thermal stability of the nanocapsules was analysed by differential scanning calorimetry and thermogravimetric analysis. Increasing the formaldehyde content reduced the nanocapsules' chemical stability. The capsule sizes obtained were nanometric at all melamine ? formaldehyde ratios studied, with a non‐significant variation in particle size and shape. © 2017 Society of Chemical Industry     

硼酸凝固浴对MF-PVA纤维结构与性能的影响

以三聚氰胺(M)、甲醛(F)、聚乙烯醇(PVA)水溶液为原料反应制得纺丝原液,经湿法纺丝得到三聚氰胺甲醛-聚乙烯醇(MF-PVA)纤维。研究了在凝固浴中加入硼酸对MF-PVA纤维结构及性能的影响。采用凯氏定氮法、扫描电子显微镜、单纤电子强力仪和极限氧指数(LOI)仪表征了纺丝过程氮流失率、纤维形貌结构、力学性能以及阻燃性能。结果表明:在凝固浴中加入硼酸可以有效地控制MF树脂的溶出,随着硼酸添加量的增加,纤维的氮流失率明显降低,断裂强度增加,断裂伸长率减小,LOI提高。当添加硼酸的质量分数为7%时,纤维的氮流失率只有14.64%,其LOI达到40%,但纤维表面变得粗糙。     

Effect of boric acid and melamine on the intumescent fire‐retardant coating composition for the fire protection of structural steel substrates

Intumescent coating is an insulating material designed to decrease heat transfer to a substrate structure. The coating presented in this research article was based on expandable graphite, ammonium polyphosphate, melamine, and boric acid. Bisphenol A epoxy resin BE‐188 was used as a binder with ACR hardener H‐2310 polyamide amine. Different formulations were developed to study the effect of expansion and heat shielding after fire testing. The coating was tested at 950°C for 1 h. The results show that the coating was stable and well bonded with the substrate. The coating was characterized with thermogravimetric analysis (TGA, Parkin Elmer, Norwalk, CT, 06859, USA), Fourier transform infrared (FTIR, Nicolet 400 D Shimadzu spectrometer) spectroscopy, X‐ray diffraction (XRD, Bruker D8 advance Diffracto meter, Bruker Germany), and scanning electron microscopy (SEM, Carl Zeiss Leo 1430VP, UK). The morphology of char was studied by SEM on the coating after fire testing. XRD and FTIR spectroscopy showed the presence of graphite, boron phosphate, boron oxide, and sassolite in the residual char. TGA (Pyris 1, manufactured by Parkin Elmer, Norwalk, CT, 06859, USA) and differential thermal gravimetric analysis (DTGA) showed that boric acid enhanced the residual weight of the intumescent fire‐retardant coating. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Studies on synthesis,characterization, and metal adsorption of mimosa and valonia tannin resins

A few thermosetting wood adhesive tannin resin system from formaldehyde reaction with both condensed and hydrolysable tannin has been developed. Polymerization of formaldehyde with mimosa tannin and valonia tannin was carried out at optimal conditions obtained from literature to establish the adhesive resin formulation. Formed reaction products were characterized by FTIR spectroscopy. The possible adsorption mechanisms for the adsorption of various metal ions onto tannin‐formaldehyde resins were proposed. Also, thermal analysis were studied and discussed by differential scanning calorimetry and thermogravimetry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 786–797, 2006     

Synthesis,characterization, and performance evaluation of hard,anticorrosive coating materials derived from diglycidyl ether of bisphenol A acrylates and methacrylates

Diglycidyl ether of bisphenol A acrylate (DAC) and diglycidyl ether of bisphenol A methacrylate (DMAC) were synthesized by the reaction of an epoxy [diglycidyl ether of bisphenol A (DGEBA)] with acrylic acid and methacrylic acid, respectively. The synthesized resins were characterized by determination of the acid, hydroxyl, and saponification values. Structure elucidation was done by gel permeation chromatography, Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, and ¹³C‐NMR spectroscopy. DACs were cured with melamine formaldehyde resin at low pH values. The pH of the resin systems was adjusted with phosphoric acid. The coatings of these systems were formed on mild steel specimens for physicomechanical and chemical/corrosion‐resistance performance. The coatings of DAC and DMAC showed excellent scratch hardness and good impact‐resistance performance. The coatings of DMAC showed better performance than DAC with respect to chemical and corrosion resistance. Thermogravimetric analysis and differential scanning calorimetry were used to investigate the thermal stability and curing behavior of these systems. DAC showed a little higher glass‐transition temperature than DMAC and also showed a higher thermal resistivity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 494–501, 2005     

本期特约专栏主持人——张斌教授：原位生成SiO2改性硼硅酚醛树脂的合成与性能研究

在合成酚醛树脂的过程中引入有机硅预聚物和硼酸,制得硼硅酚醛树脂,并在此基础上加入正硅酸乙酯,原位水解生成SiO2,进一步改性了硼硅酚醛树脂。分别考查了有机硅预聚物、硼酸和正硅酸乙酯加入量对改性酚醛树脂粘接强度的影响。通过IR考查了改性树脂的结构,硼氧键和硅氧键成功地引入到酚醛树脂中。还通过DSC和不同条件下粘接强度的测试考查了改性树脂的固化性能,确定了其固化工艺。空气气氛中的热重分析则表明改性酚醛树脂初始分解温度为475℃,1000℃残炭率为21％,耐热性明显优于普通酚醛树脂。     

Preparation,characterization, and composites from low formaldehyde emission urea–formaldehyde–casein copolymer

A modified urea–formaldehyde resin was synthesized by the condensation of urea and formaldehyde in the presence of varying proportions of casein up to 25% (w/w) of urea under alkaline conditions. All the prepared resins were characterized by free‐formaldehyde content, viscosity measurements, and number‐average molecular weight determination by vapor pressure osmometry and IR spectroscopy. Their curing kinetics were studied isothermally and by differential scanning calorimetry on dynamic runs. The resin samples were cured isothermally at 60, 80, and 100°C using ammonium chloride and hydroxylamine hydrochloride as curing agents. The isothermal curing study was also performed with hexamine at 120°C. Cured resins were characterized by IR and thermogravimetric analysis. The resin samples were employed for the fabrication of glass fiber and jute fiber reinforced composites by maintaining 2 : 3 and 3 : 2 proportions of resin/reinforcement, respectively. The prepared composites were tested for their mechanical properties and resistance toward various chemicals. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 531–537, 2005     

硼酸交联线性酚醛树脂的研究

研究了硼酸与六亚甲基四胺对线性酚醛树脂的交联反应。试验结果显示,当m酚醛树脂：m六亚甲基四胺=85：10：5时．经热压成型所得样品具有较好的力学性能;FT-IR分析显示,样品中已形成B-O-C键;TG分析表明,随着硼酸含量的增大．样品的失重率逐渐降低,大大提高了酚醛树脂的耐热性。     

含硼苯并噁嗪玻璃布层压板的研制

以甲醛、苯酚、硼酸和二元胺为原料合成了含硼苯并噁嗪树脂(BBZ)。采用核磁共振仪、红外光谱仪、DSC及TGA分析研究了BBZ树脂的结构,树脂及其固化物(PBBZ)的热性能,并对树脂溶液和浸胶布的性能以及层压板的力学和电性能进行了测试。结果表明,BBZ具有较好的热稳定性;PBBZ的玻璃化温度(Tg)为183℃,并具有优良的热分解稳定性,5%热失重温度为423℃,800℃残炭率为65%。其层压板具有较好的热态保持率(180℃为74.5%,200℃为58.9%),燃烧等级达到V-0级,同时具有较好的电性能和力学性能。     

Synthesis of acetophenone formaldehyde resin containing ABA type block copolymers by ATRP

Well‐defined ABA type block copolymers of acetophenone formaldehyde resin (AFR) and methyl methacrylate (MMA) were synthesized via atom transfer radical polymerization. In the first step, acetophenone formaldehyde resin containing hydroxyl groups was modified with 2‐bromopropionyl bromide. Resulting difunctional macroinitiator was used in the ATRP of MMA using copper bromide (CuBr)/N,N,N′,N″,N″‐pentamethyl‐diethylenetriamine (PMDETA) as the catalyst system at 90°C. The chemical composition and structure of the copolymers were characterized by nuclear magnetic resonance (¹H‐NMR) spectroscopy, Fourier transform infrared (FT‐IR) spectroscopy, and molecular weight measurement. Gel permeation chromatography (GPC) was used to study the molecular weight distributions of the AFR block copolymers. M_n up to 24,000 associated with narrow molecular weight distributions (PDI < 1.5) were obtained with conversions up to 79%. Coating properties of obtained block copolymers such as adhesion and reflectance values were investigated. They showed good adhesion properties on Plexiglass substrates. Reflectance values increased as the resin content of polymer increased. The thermal properties of all polymers were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). All block copolymers showed higher thermal stability than their precursor AFR resin. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

In Situ preparation of resol/clay nanocomposites

In this study, in situ modified phenol formaldehyde resins were prepared from hydroxyl terminated polydimethyl siloxane (DH.PDMS), clay (montmorillonite) in the presence of base catalyst. Different clay contents (0.5, 1, 3, 5 wt %) were used to produce DH.PDMS modified resol/clay nanocomposite resins (DH.PDMS‐LC‐PFRs). DH.PDMS‐LC‐PFRs were partially cured by heat, and the effects of the curing process and the clay content in the resol resin were determined on the spectroscopic, thermal, mechanical and microscopic properties of the final products. Furthermore, the effects of the reaction time on the polymerization and on the morphology of the materials were investigated. The structures of the specimens were characterized by means of Fourier Transform Infrared (FTIR‐ATR) spectroscopy. Thermal properties of the samples were determined with Differential Scanning Calorimeter (DSC) and Thermogravimetric Analyzer (TGA). Mechanical properties of the specimens were determined by Dynamic Mechanical Analyzer (DMA). The obtained samples were also characterized morphologically by Scanning Electron Microscope (SEM). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013