Phenol Urea Formaldehyde Resin Research Articles

Surface characteristics of phenolic resin coatings

Phenolic resins are commonly used as polymer binders for metal, paper and mineral wool substrates. For such applications, mechanical, adhesive and thermal properties are considered most important, and the effect of synthesis and structural parameters on such end-use characteristics are well-documented. However, surface characteristics of cured phenolic resins can be equally relevant and are often overlooked. Widely used resins are phenol-urea-formaldehyde (PUF) and phenol-formaldehyde (PF). It is believed that the inherent chemistry and curing procedure of these resins result in coatings with distinct surface properties and wettability. To gain more insight into surface characteristics such as morphology, chemical composition and wettability of cured PUF and PF resins, different binder formulations were applied on glass substrates and subsequently characterised by Scanning Electron Microscopy (SEM), Contact Angle Goniometry (CAG) and X-Ray Photoelectron Spectroscopy (XPS). The effect of catalyst, chemical composition and curing conditions on surface characteristics of various PUF and PF coatings were investigated. The curing temperature was found to have a strong influence on surface properties; curing at 200 °C yields a surface with varying degrees of oxidation, differences in linkages between phenolic and urea species, and a lower overall nitrogen content in case of urea-containing coatings, resulting in stronger fluctuations in water-wettability compared to surfaces hardened at lower temperatures.

Wood modification with phenol urea formaldehyde (PUF) resin: the influence of wood species selection on the dimensional stability

Wood modification is an excellent way to improve material properties, prolong service life, and pave the way for new applications for timber in the built environment. The aim of this study is to establish the influence of wood species in the modification process with phenol urea formaldehyde resin. Seven hardwoods and four softwoods were compared in an identical treatment. Since the wood species is the main variable, the study provides a clear insight as to its influence on modification—something not previously investigated. Small wood blocks of all eleven species were impregnated with low-molecular weight phenol urea formaldehyde resin and were subsequently heat-cured at 150 °C. Mass and dimensions of specimens were carefully monitored throughout three cycles of oven-drying and water-soaking to determine anti-swelling efficiency, bulking coefficient, and swelling coefficient. The results showed a clear relationship between density, bulking-, and swelling coefficients. Beyond this well-known relationship it was observed that species with similar density (e.g., lime and sycamore) had significantly different bulking coefficients and anti-swelling efficiencies. Reasons for these differences, which are independent of density, are discussed. The soaking solution was analysed to determine the nature of leached substances showing a correlation between the amount of leachate and the UV-absorbance (272 nm) of the solution.

Nitrogen-containing high surface area carbon cryogel from co-condensed phenol–urea–formaldehyde resin for CO2 capture

A cost-effective nitrogen-doped super high surface area carbon cryogel has been successfully synthesized from phenol–urea–formaldehyde (PUF) resin. Pore structure and chemical characteristics were investigated using scanning electron microscopy, Fourier transform infrared spectroscopy, element analysis, X-ray photoelectron spectrometry, mercury porosimetry and N2 adsorption–desorption. It was found that the organic cryogel with mesopores and macropores from PUF resin having a N content of 9.03 wt%, which is an ideal precursor for preparing N-doped carbon cryogels. The carbon cryogel obtained having a high apparent surface area of up to 1710 m2/g, large micropore volumes up to 0.64 cm3/g, a small average micropore width of 1.04 nm and a moderate nitrogen content of 2.08 wt%. The lab-made carbon cryogel showed good CO2/N2 sorption selectivity, 15.8:1 at 273 K and 16.4:1 at 298 K. The CO2 capture capacities as high as 5.5 mmol/g at 273 K and 4.5 mmol/g at 298 K up to 1 bar were obtained, which were among the highest compared to other commercial carbon materials.

Eco-Friendly Phenol-Urea-Formaldehyde Co-condensed Resin Adhesives Accelerated by Resorcinol for Plywood Manufacturing.

Eco-friendly and good-performance resin adhesives are needed for wood manufacturing. In this study, phenol–urea–formaldehyde (PUF) resin adhesives were modified by adding various ratios of resorcinol. The properties of PUF, phenol–resorcinol–urea–formaldehyde (PRUF) resin adhesives, and the performances of the prepared plywood were tested. The curing behaviors and the structural features of the PUF and PRUF resin adhesives were investigated via dynamic scanning calorimetry, thermal gravimetric analysis, 13C NMR, and cross polarization magic angle spinning 13C NMR. The results indicated that 1.3% resorcinol (based on resin, w/w) could decrease the curing temperature and accelerate the curing process after PUF resin modification. The PRUF resin adhesives demonstrated a lower activation energy during the curing process, with up to 28.8% less energy than that of PUF resin adhesive without any curing agent. The plywood demonstrated low formaldehyde emissions (<0.1 mg L–1) and acceptably high bonding strengths (>1.00 MPa). This work provided a method for preparing an easy-cured and high-performance phenolic resin for wood manufacturing.

Phenol–urea–formaldehyde resin co-polymer synthesis and its influence on Elaeis palm trunk plywood mechanical performance evaluated by 13C NMR and MALDI-TOF mass spectrometry

This study evaluated a new method of producing phenol–urea–formaldehyde (PUF) adhesives formulated differently under actual “in-situ” resin synthesis conditions. This was carried out by co-polymerizing urea formaldehyde (UF) resin with phenol–formaldehyde resin in the core layer of low molecular weight (LMW) phenol–formaldehyde (PF) resin treated Elaeis palm trunk veneers during the gluing process of Elaeis palm plywood. Matrix assisted laser desorption Ionization time of flight (MALDI-TOF) mass spectrometry (MS) illustrated and confirmed a series number of the phenol–urea co-condensates repeating unit in the prepared PUF resins which corroborated well with its mechanical properties (modulus of elasticity and modulus of rupture), bonding quality (dry test and weather boil proof or WBP test) and physical properties. A series of PF, UF and PUF resins oligomers forming repeating units up to 1833Da were identified. Besides that, the solid state 13Carbon nuclear magnetic resonance (NMR) interpretation identified that the signal at 44–45ppm and 54–55ppm corresponding to methylene bridges were co-condensated in between phenol and urea in the PUF resin system. The 13C NMR investigation showed that the synthesis process of PUF resin contained no free formaldehyde elements. Furthermore, the proportion of urea and methylolureas in the mixture to synthesis PUF resin were sufficient and incorporated well into the formulation by reacting with LMWPF units to form co-condensed methylene bridges. This study showed a new and useful method to synthesize PUF resin during the gluing process of manufactured Elaeis palm plywood which can also enhance the performance of Elaeis palm plywood panels for structural instead of utility grade applications.

Effects of surfactants on the mechanical properties, microstructure, and flame resistance of phenol–urea–formaldehyde foam

To study the effect of surfactants on the foaming behavior of phenol–urea–formaldehyde foam, silicone oil (Dow Corning DC-193) and Tween-80 surfactants were selected to study their effects on the mechanical properties, microstructure, and combustion characteristics of the foams. The results show that the surface tension of the phenol–urea–formaldehyde resins decreased with increasing surfactant concentration. Both the foaming temperature and foaming capacity of the phenol–urea–formaldehyde foam first increased and then decreased with increasing surfactant concentration. The compressive strength and oxygen index of the phenol–urea–formaldehyde foam first decreased and then increased with increasing surfactant concentration, which is probably related to the foaming capacity of the foam. The microstructure of the foams showed that the average pore diameters first increased and then decreased with increasing surfactant concentration. The combination of DC-193 and Tween-80 surfactants significantly improved the compressive strength, uniformity of the cells, and the number of closed cells in the final foam product.

Formaldehyde emissions from particle board made with phenol–urea–formaldehyde resin prepared by different synthesis methods

This paper suggests the optimum NAF resin preparation to reduce the quantity of pollutant emissions from the particle boards by using PUF resin. The pollutant emissions performance of the prepared NAF resin was evaluated by comparison with eMDI resin. Each PF and PUF resin was made by variation of the molar ratio and synthesis methods according to order of addition of the basic products. In addition, after verifying the properties of the resins, the quantity of pollutant emitted from boards made with the PUF resins were evaluated. Of the cases of boards made with each resin, the formaldehyde emission was the lowest for PB #7. The eMDI resin used in this board showed good quality as an eco-friendly resin, because it had less than half the formaldehyde emission of the other formaldehyde-based resins. In addition, the mechanical properties of the particle board met the KS criteria; therefore, there should be no restriction on use in manufactured goods.

Synthesis of novel monolithic activated carbons from phenol–urea–formaldehyde resin

Phenol–urea–formaldehyde (PUF) organic foams have been firstly synthesized from phenol–urea–formaldehyde resin under alkaline conditions, which can be used as precursor to produce cellular activated carbon foams.

Synthesis and Comparison of Phenol-Urea-Formaldehyde (PUF) Thermosetting Resin with Commercial Synthetic Resins

Phenol-urea-formaldehyde (PUF) thermosetting resin was synthesized by reacting methylol phenol with urea under acidic condition and its bonding strength was compared with commercial synthetic resins (PF resin, UF resin and PUF resin made by mechanical blending of PF and UF resins). The results indicated that PUF resin made by this process performed better bonding strength than commercial UF resin and mechanical blending of PF and UF resins in both dry and wet conditions. Its bonding strength was found to be intermediate to UF and PF resins.

13C NMR study on the structure of ZnO-catalyzed phenol–urea–formaldehyde resin during its synthesis process

The structure of ZnO-catalyzed phenol–urea–formaldehyde (PUF) resin at different synthesis stages was analyzed by liquid 13C nuclear magnetic resonance spectroscopy. The results showed that the general structure of ZnO-catalyzed PUF resin was almost the same as the control PUF resin. Addition reaction between phenol and formaldehyde mainly occurred at the first stage. Total methylol groups amount between phenols of the control resin was a little lower than that of the ZnO-catalyzed PUF resin. Co-condensation and self-condensation reaction occurred at the second stage. The preparation method of ZnO-catalyzed PUF resin favored the co-condensation reaction between phenol methylol groups and urea units, while self-condensation reaction dominated the control resin at the second stage. Formaldehyde completely reacted for both the control and ZnO-catalyzed PUF final resin. The total amount of methylol and methylene groups between urea units and phenols, respectively, was almost the same for the two final resins. The total quantity of methylol groups between phenols represented a continuing downward trend from the first stage to the final stage, and the amount of methylol group (p-Ph–CH2OH) of ZnO-catalyzed PUF resin was 30% more than that of the control resin. Total co-condensed methylene groups amount of ZnO-catalyzed PUF resin was greater than that of the control resin, which indicated that ZnO could make the urea units well incorporated into the co-condensed PUF resin.

Synthesis and Structure Characterization of Phenol-Urea-Formaldehyde Resins in the Presence of Magnesium Oxide as Catalyst

The objective of this research was to provide a useful approach of polymer synthesis for accelerating the fast cure of phenol-urea-formaldehyde (PUF) resin as wood adhesive by optimizing its structure and composition. The PUF resins containing high contents of very reactive groups such as para-methylol groups were synthesized by reacting methylolurea, phenol, and formaldehyde in the presence of magnesium oxide (MgO) as catalyst. The effects of synthesis parameters including F/(P + U), OH/P, and MgO/P mole ratios on the structure, composition, curing characteristics, and their relationships of PUF resins were investigated. The results indicated that MgO seemed to be an efficacious catalyst for PUF resin synthesis and promote its faster cure. The increase in the F/(P + U) mole ratio or/and OH/P mole ratio appeared to be beneficial for the formation of para-methylol groups and cocondensed methylene linkages between phenolic methylol groups and urea units, and for the removal of unreacted urea. In case of Catalyst/P mole ratio, an appropriate dosage of added metal-ion was very important for synthesizing the high-content reactive groups of PUF resins, otherwise leading to the reverse effects.

Ordered nitrogen doped mesoporous carbon assembled under aqueous acidic conditions and its electrochemical capacitive properties

With urea as nitrogen source, soluble phenol–urea–formaldehyde (PUF) resin is synthesized under basic conditions, and then an N-containing mesophase is obtained by co-assembly of the obtained PUF resin and block copolymer of F127 in acidic aqueous solution. The pyrolysis of the resultant mesophase in inert atmosphere produces a nitrogen-doped mesoporous carbon, which possesses a well-defined ordered mesoporous structure, large surface area (up to 537m2/g), uniform pore size (∼3.6nm) and large pore volume (∼0.49cm3/g). Multi-techniques, such as elemental analysis, X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDS) are performed to characterize the samples; these analytic results indicate that the doped nitrogen mainly exists as pyridinic and pyrrolic nitrogen is successfully and homogeneously introduced into the skeleton of the mesoporous carbon. And more, the nitrogen content in the final ordered mesoporous carbon can be easily adjusted up to 3.85 wt.% by increasing the original ratio of urea to phenol. Electrochemical measurements show the nitrogen doped mesoporous carbon presents a higher specific capacitance (up to 225F/g) than nitrogen-free ones (169F/g) and exhibits a good electrochemical stability even after 1000 cycles at current density of 5.0A/g.

Synthesis and characterization of phenol‐urea‐formaldehyde foaming resin used to block air leakage in mining

In this study, phenol, urea, and paraformaldehyde were used as the monomers for the one‐step synthesis of phenol‐urea‐formaldehyde (PUF) foaming resin that was used to block air leakage in mining. An orthogonal test was used to study the effects of urea amount, catalyst amount, reaction temperature, and reaction time on the foaming property of the resin. The results showed that the optimum parameters for synthesizing PUF resin are as follows: 1 mol phenol, 0.5 mol urea, 3 mol formaldehyde equivalents of paraformaldehyde, and 0.05 mol catalyst at 75°C for 3 h. The infrared and 13C nuclear magnetic resonance spectra of the PUF resin showed that the chemical structure of the PUF resin was significantly different from that of phenol‐formaldehyde resin, indicating that a copolymerization reaction has occurred among the three components, that is, phenol, urea, and paraformaldehyde. In this study, PUF foam was prepared from catalysts and PUF resin. The results showed that the foaming capacity and oxygen index of the PUF foam were significantly improved by using urea, whereas the shrinking percentage decreased with no change in compression strength. POLYM. COMPOS., 35:2056–2066, 2014. © 2014 Society of Plastics Engineers

Co-polymerization analysis of thermosetting resins using1H-15N-13C triple resonance NMR spectroscopy

1H-15N-13C correlation NMR spectroscopy techniques developed to identify and characterize co-polymer fragments in melamine-urea-formaldehyde (MUF) and phenol-urea-formaldehyde (PUF) model systems have been applied to industrially prepared MUF, PUF, and phenol-melamine-formaldehyde (PMF) resins. The NMR data confirm that co-polymers form in a commercially prepared MUF resin manufactured by Momentive Specialty Chemicals Pty. Ltd. Spectra from PUF model reactions were compared with those from a PUF resin and it was determined that PUF co-polymers did not form in the resin prepared using typical temperature and pH. Finally, NMR spectroscopy was used to identify and characterize PMF co-polymer bonds in a phenol-melamine-urea-formaldehyde (PMUF) resin prepared using a procedure from Momentive Specialty Chemicals Pty. Ltd. With these NMR techniques in hand, it is now possible to relate co-polymer structures to properties of commercial thermosets. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Effect of Synthesis Conditions on the Structure and Curing Characteristics of High-Urea Content PUF Resin

Phenol-urea-formaldehyde (PUF) resins of high urea content were prepared at different hydroxyl/phenol (OH/P) mole ratios and formaldehyde/(phenol + urea) [F/(P + U)] mole ratios. The effect of synthesis parameters including OH/P and F/(P + U) mole ratios on the structure, composition, and curing characteristics of PUF resins were investigated by using both liquid 13C nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). The NMR analysis indicated that an increase in the OH/P mole ratio and/or F/(P + U) mole ratio decreased the amount of unreacted urea and monosubstituted urea, and promoted the formation of polysubstituted urea. The DSC results showed that the higher OH/P mole ratio and/or F/(P + U) mole ratio of PUF resins resulted in a lower curing temperature. The F/(P + U) mole ratio of PUF resins seemed to have a more significant accelerating effect on the curing reaction than the OH/P mole ratio.

Cure properties and adhesive performances of cure-accelerated phenol-urea-formaldehyde resins

The cure properties of cure-accelerated phenol-urea-formaldehyde (PUF) resins with different catalysts [calcium oxide (CaO), sodium carbonate (Na2CO3), zinc oxide (ZnO), and magnesium oxide (MgO)] were investigated by gelation test and differential scanning calorimetry (DSC) analysis. The results indicated that catalysts such as Na2CO3, ZnO, and MgO were capable of increasing the curing rate and decreasing the curing temperature of PUF resins, however, the CaO inhibited the cure reaction. The formation of methylene bridges was considered to be the main reaction during curing. For the ZnO- and MgO-accelerated PUF resins, the addition reaction of formaldehyde with free phenolic site may act as subsidiary reaction. The activation energies (E a ) of cure-accelerated PUF resins other than CaO-acceleration were much lower than the control resin. The effects of catalysts and hot press temperature on adhesive performances of PUF resins were also discussed by plywood test. The PUF resins with Na2CO3, ZnO, and MgO had higher wet shear strength than the control resin. Hot press temperature had a strong influence on the wet shear strength as well as the catalysts. Among the catalysts, MgO had more significant improving effect on both the curing process and the wet shear strength of PUF resin.

On the structure and cure acceleration of phenol–urea–formaldehyde resins with different catalysts

Phenol–urea–formaldehyde (PUF) resins with different catalysts [calcium oxide (CaO), sodium carbonate (Na 2CO 3), zinc oxide (ZnO), and magnesium oxide (MgO)] were prepared to accelerate the cure of the resin at low temperature. The cure-acceleration effects of catalysts on chemical structure and cure characteristics of PUF resins were investigated by using both liquid 13C nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). The liquid 13C NMR analysis indicated that the catalyst such as CaO seemed to present a retarded effect on the polycondensation reaction of phenolic components with urea units, while the Na 2CO 3 appeared to promote the self-condensation reaction of phenolic methylol groups at para position toward the formation of para– para methylene linkage. Both ZnO and MgO in PUF resins promoted self-condensation reaction of para methylol groups and condensation reaction of ortho methylol groups with para methylol groups. The catalysts such as Na 2CO 3, ZnO, and MgO can make PUF resins cure at a low temperature. Among these catalysts, the MgO had the most significant accelerating effect on polycondensation and cure reaction of PUF resin.

Synthesis–structure–performance relationship of cocondensed phenol–urea–formaldehyde resins by MALDI‐ToF and 13C NMR

AbstractMatrix assisted laser desorption ionization time of flight (MALDI‐ToF) mass spectrometry has consistently confirmed on a number of PUF resins that phenol–urea cocondensates exist in phenol–urea–formaldehyde (PUF) resins. A noticeable proportion of methylene‐linked phenol to urea cocondensates were detected in all the PUF resins tried, alongside methylene bridges connecting phenol to phenol and urea to urea. The PUF, PF, and UF oligomers formed were identified. Variations of the PUF preparation procedure did always yield a certain proportion of the mixed phenol to urea cocondensates. Their relative proportion was determined and related the synthesis procedure used. Comparison of the MALDI‐ToF results with a 13C NMR investigation showed that in a real PUF resin in which phenol to urea cocondensates were identified the methylene bridge NMR signal at 44 ppm, characteristic of phenol to urea unsubstituted model compound cocondensates, does not appear at all. This confirmed that this peak cannot be taken as an indication of the existence of phenol and urea condensation under actual resin preparation conditions. The peak indicating cocondensation in PUF resins in which the phenolic nuclei and urea are substituted appears instead at 54.7–55.0 ppm. Thermomechanical analysis has again confirmed that the resin gel times greatly accelerates with increasing urea molar content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Characterization of phenol–urea–formaldehyde resin by inline FTIR spectroscopy

AbstractPhenol–urea–formaldehyde (PUF) resins were synthesized by a two‐step polymerization process. The first step was the synthesis of 2,4,6‐trimethylolphenol (TMeP) from phenol and formaldehyde, under alkaline conditions. In the second step PUF resins were synthesized by the reaction of TMeP with urea, under acidic and alkaline conditions. The influence of temperature on the synthesis of TMeP was investigated. The molar ratio between TMeP and urea was varied to study the composition effect on the second step of the PUF synthesis and final product properties. Synthesis of TMeP and PUF resins were monitored by inline FTIR‐ATR system. Analytical methods, such as differential scanning calorimetry, nuclear magnetic resonance, thermogravimetric analysis, and infrared spectroscopy were used for characterization of TMeP and PUF resins. Obtained PUF resins were cured and tested on flexural strength. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006

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

AbstractThe 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 (Ttanδ) 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 Ttanδ 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 Ttanδ 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 Ttanδ 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