Copolymer of ketonic resin–polyacrylonitrile

The polymerization of acrylonitrile in the presence of Ce(IV) salts and ketonic resin such as methyl ethyl ketone/formaldehyde and cyclohexanone/formaldehyde resin was investigated. Block copolymer of ketonic resin–polyacrylonitrile was produced. The effect of Ce(IV) concentration, temperature, time, and monomer concentration on the yield and molecular weight was studied. Maximum yield was obtained at 50°C and ceric ammonium nitrate concentration of 0.033 mol/L.     

Soluble polypyrrole copolymers

A new class of dimethyl formamide (DMF)– and acetone‐soluble conducting pyrrole–ketonic resin copolymers has been developed. This was accomplished by oxidatively polymerizing pyrrole monomer by Ce(IV) salt in the presence of methyl ethyl ketone formaldehyde resin (MEKF–R). The resulting copolymers were readily dissolved in DMF and acetone. These products were characterized by FTIR and UV‐visible spectroscopy, conductivity, four‐probe conductivity, viscosity, and DSC measurements. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1098–1106, 2001     

New melamine–formaldehyde–ketone polymers. II. Dissolution of melamine in reactive solvents prepared from cyclohexanone

Reactive solvents of melamine were prepared from cyclohexanone and excess of formaldehyde in the presence of triethylamine catalyst. The solubility of melamine in the solvents was evaluated and the mechanism of dissolution explained on the basis of ¹H‐NMR and IR spectroscopy. Attempts to cure the melamine solutions resulted in melamine–formaldehyde–cyclohexanone polymers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 77–85, 2005     

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.     

In situ modification of cyclohexanone formaldehyde resin with boric acid for high‐performance applications

A boron‐containing cyclohexanone formaldehyde resin (BCFR) was synthesized from cyclohexanone, formaldehyde, and boric acid. The effects of the boric acid concentration, solubility, molecular weight, and thermal properties on the product were investigated. Characterization of the BCFRs was done by NMR spectroscopy, gel permeation chromatography, and Fourier transform infrared–attenuated total reflectance spectroscopy. The thermal properties of the samples were determined with differential scanning calorimetry and thermogravimetric analysis. The study results demonstrate that the resin had higher heat‐resistance properties than the commonly modified cyclohexanone formaldehyde resin. The obtained samples were also characterized morphologically by scanning electron microscopy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

New melamine‐formaldehyde‐ketone polymers: I. Synthesis of reactive solvents of melamine from selected ketones

Reactive solvents of melamine were prepared by reacting ketones with an excess of formaldehyde in the presence of triethylamine catalyst. The ketones used were cyclohexanone, cyclopentanone, acetophenone, benzoylacetone, biacetyl, or ethyl‐methyl ketone. The structures of the resulting reactive solvents were studied by ¹H‐NMR. The best solubility of melamine was observed for the solvent derived from ethyl‐methyl ketone. Preliminary attempts at curing the melamine solutions yielded melamine‐formaldehyde‐ketone polymers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95:1319–1332, 2005     

New melamine–formaldehyde–ketone polymers. III. Coatings from melamine and reactive solvents based on cyclohexanone

The conditions and methods of preparing novel melamine–formaldehyde–cyclohexanone coatings are presented. The coatings were prepared by dissolving melamine in reactive solvents based on formaldehyde and cyclohexanone. The latter were prepared at different molar ratios of the components. The water resistance of the resulting coatings was measured. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1083–1092, 2006     

Modification of cyclohexanone–formaldehyde resins with silicone tegomers

Cyclohexanone–formaldehyde resins were modified in situ with α,ω‐diamine polydimethylsiloxanes and α,ω‐dihydroxy polydimethylsiloxanes. Melting points, solubilities in organic solvents, gel permeation chromatographs, Fourier transform infrared spectra, and NMR spectra of the modified resin were determined, and the surface properties of the resins were investigated by contact angle measurements. A small amount of silicon compounds seemed to effect the physical properties of the cyclohexanone–formaldehyde resins significantly. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 97–101, 2005     

Soluble and conductive polypyrrole copolymers containing silicone tegomers

Soluble and processable conductive copolymers of silicone tegomers and pyrrole were developed. This was easily accomplished by the oxidative polymerization of pyrrole monomer by Ce(IV) salt in the presence of silicone tegomers with hydroxyl chain ends. The resulting copolymers were soluble in dimethylformamide. The products were characterized by Fourier transform infrared, ¹H‐NMR, and four‐point probe conductivity, and their surface properties were investigated with contact‐angle measurements. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2896–2901, 2003     

Soluble and conductive copolymers from 1‐(hydroxyalkyl) pyrroles

1‐Substituted pyrroles such as 1‐(hydroxymethyl)pyrrole, 1‐(3‐hydroxypropyl) pyrrole, 1‐H‐1‐pyrrolylmethyl 4‐methyl‐1‐benzenesulfonate, 1‐H‐1‐pyrrolylpropyl 4‐methyl‐1‐benzenesulfonate, and 1‐H‐pyrrolylmethyloctanoate were synthesized and oxidative polymerized and copolymerized with pyrrole by using (NH₄)₂Ce(NO₃)₆ and FeCl₃. Some of the copolymers were slightly soluble in DMF and DMSO. The products were characterized by FTIR, ¹H‐NMR, and four‐point probe conductivity. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1830–1834, 2005     

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.     

Ketonic resins as free radical photoinitiators

Photoreactive cyclohexanone‐formaldehyde and acetophenone‐formaldehyde resin‐bound benzoin and benzoin isobutyl ether resins were successfully prepared by the method of in situ modification of ketonic resins. These photoinitiators were used to polymerize styrene using UV lamp with wavelength of 350 nm. Initiating efficiencies of ketonic resin‐bound benzoin and benzoin ether were much higher than benzoin and benzoin ether. The products were ketonic‐resin‐polystyrene block copolymers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 927–934, 1999     

Solubilization of nitrogen‐containing heterocyclic compounds in reactive solvents

A reactive solvent was obtained by reacting 1 mol of cyclohexanone with 5 mol of formaldehyde. The structure of the solvent was studied by using ¹H‐NMR and IR spectroscopy. It was used for solubilization of melamine and other heterocyclic compounds containing ? NH? groups, such as adenine, carbazole, cytozine, guanine, thymine, and uracyl, as well as isocyanuric, barbituric, and uric acids. The solubilization involved the reaction of formaldehyde (liberated at an elevated temperature) with amino groups of the compound. Melamine was the compound with the best solubility in the reactive solvent. Preliminary attempts of curing the solutions have also been made. The oligomers cured at 120°C in the presence of acidic catalysts. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2650–2659, 2002     

Influence of the synthesis conditions on the curing behavior of phenol–urea–formaldehyde resol resins

The curing behavior of synthesized phenol–urea–formaldehyde (PUF) resol resins with various formaldehyde/urea/phenol ratios was studied with differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The results indicated that the synthesis parameters, including the urea content, formaldehyde/phenol ratio, and pH value, had a combined effect on the curing behavior. The pH value played an important role in affecting the shape of the DSC curing curves, the activation energy, and the reaction rate constant. Depending on the pH value, one or two peaks could appear in the DSC curve. The activation energy was lower when pH was below 11. The reaction rate constant increased with an increase in the pH value at both low and high temperatures. The urea content and formaldehyde/phenol ratio had no significant influence on the activation energy and rate constant. DMA showed that both the gel point and tan δ peak temperature (T_tanδ) had the lowest values in the mid‐pH range for the PUF resins. A different trend was observed for the phenol–formaldehyde resin without the urea component. Instead, the gel point and T_tanδ decreased monotonically with an increase in the pH value. For the PUF resins, a high urea content or a low formaldehyde/phenol ratio resulted in a high gel point. The effect of the urea content on T_tanδ was bigger than that on the gel point because of the reversible reaction associated with the urea component. Too much formaldehyde could lead to more reversible reactions and a higher T_tanδ value. The effects of the synthesis conditions on the rigidity of the cured network were complex for the PUF resins. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1368–1375, 2005     

Block copolymers of cyclohexene oxide and ketonic resins via condensation and promoted cationic polymerization

Block copolymers of cyclohexene oxide (CHO) and ketonic resin were prepared by using ketonic resins as free radical photoinitiators via two‐step procedure. In the first step, cyclohexanone–formaldehyde and acetophenone–formaldehyde resins were modified during their preparation with benzoin and benzoin isobutyl ether. Then, AB or ABA type block copolymers depending on the resin employed were obtained by irradiation of these resins in the presence of pyridinium salt and CHO as a cationically polymerizable monomer. By this way, block copolymers of CHO with ketonic resin were prepared and characterized by GPC, DCS, FTIR, and ¹H NMR spectral measurements. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Differential scanning calorimetry characterization of urea–formaldehyde resin curing behavior as affected by less desirable wood material and catalyst content

Differential scanning calorimetry was applied to investigate the curing behavior of urea–formaldehyde (UF) resin as affected by the catalyst content and several less desirable wood materials (e.g., wood barks, tops, and commercial thinnings). The results indicate that the reaction enthalpy of UF resin increased with increasing catalyst content. The activation energy and peak temperature of the curing UF resin generally decreased with increasing catalyst content at lower levels of catalyst content. However, with further increases in catalyst content, the changes in the activation energy and peak temperature were very limited to nonexistent. The hydrolysis reaction of the cured UF resin occurred during the latter stages of the curing process at both lower level (<0.2%) and higher level (>0.7%) catalyst contents. This indicates that there existed an optimal range of catalyst content for the UF resin. The curing enthalpy of the UF resin decreased with increasing wood raw materials present due to the effect of diffusion induced by the wood materials and the changes in the phase of the curing systems. This suggests that the curing reactions reached a lower final degree of conversion for the wood–resin mixtures than for the UF resin alone. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2027–2032, 2005     

Chain extended cyclohexanone-formaldehyde and acetophenone–formaldehyde resins

The preparation of chain extended cyclohexanone–formaldehyde and acetophenone–formaldehyde resins and their physical properties were studied. The chain extension was regulated by the ratio of the hydroxyl groups of the ketonic resin/reactive reagents. Both resins were chain extended with dimethyl dichlorosilane, phosphorus oxychloride, phenylphosphonic dichloride, toluene-2,4-diisocyanate, prepolymers (prepared from trimethylolpropane and toluene-2,4-diisocyanate), phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, 4,4′-oxydiphthalic anhydride, and maleic anhydride. Solubilities, melting point, molecular weight, and flammability of the chain extended resins were affected by the extender reagent. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 655–663, 1998     

环己酮-甲醛树脂

环己酮-甲醛树脂综合性能良好,是一种新型涂料添加剂。其生产方法有三种:甲基环己酮与甲醛共缩合;环己酮与甲醛在有机溶剂和氢氧化钠存在下一步共缩合;环己酮与甲醛在碱性条件下两步合成。工业上采用第三种方法。     

A molecular simulation study of a series of cyclohexanone formaldehyde resins: Properties and applications in plastic printing

The solubility of a series of cyclohexanone formaldehyde resins (including cyclohexanone formaldehyde resin (CFR), acetylated CFR and complete oxime of CFR) in a variety of solvents (tetrachloromethane, alcohol, toluene and ethyl ether) were studied by means of Monte Carlo approach; the free energies of mixing were estimated, which indicated results being consistent with the experimental fact. Independent cohesive energy densities (CEDs) of CFRs were computed by molecular dynamics (MD) simulation, from which we obtained the solubility parameters of CFR, acetylated CFR and complete oxime of CFR as follows, 19.45(0.22), 17.30(0.11) and 21.41(0.27) MPa^1/2. Compatibility of CFRs with a dimer acid-based polyamide (D1007E [Xiaodong Fan, Yulin Deng, John Waterhouse, Peter Pfromm. J Appl Polym Sci 1998;68:305-14.]) was estimated from the CEDs; the calculation results indicated that these three CFRs were compatible with D1007E. In addition, the interactions between coating layers (pure D1007E, D1007E with CFR, D1007E with acetylated CFR and D1007E with complete oxime of CFR, molar ratio 3:1) and a polystyrene substrate layer were investigated, in an effort to identify the effect of CFRs in plastic printing application. All the results of this work confirmed that molecular simulation techniques can be used as a tool for investigating the properties and applications of CFRs.     

Acrylonitrile polymerization initiated by Ce(IV)–cyclohexanone redox system in presence of surfactant

The rate of polymerization of acrylonitrile, using the Ce(IV)–cyclohexanone redox system as an initiator, was studied kinetically, in the presence of 0.015M sodium dodecyl sulfate (SDS), over a temperature range of 25–45°C. The rate of polymerization (R_P), percentage of monomer conversion, and rate of Ce(IV) consumption (?R_Ce) were found to increase with the concentration of SDS, above its CMC. The effect of [AN], [Ce(IV)], [H⁺], and the ionic strength were also studied. The overall activation energies for the polymerization processes were computed to be 23.14 and 17.64 kcal/mol in the absence and presence of 0.015M SDS. A suitable kinetic mechanistic scheme for the free‐radical mechanism was proposed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2066–2072, 2003