Effect of formaldehyde/phenol ratio (F/P) on the properties of phenolic resins and foams synthesized at room temperature

Six types of phenolic foaming resins were synthesized at room temperature with different formaldehyde/phenol (F/P) ratios in this study. The effects of F/P ratios on physicochemical characteristics and foaming properties of the resulting resins were analyzed based on viscosity, solids content, hydroxymethyl index, residual monomer content, molecular structure of the foaming resin, flame retardancy, and foam compression strength measurements. The results of the present study indicated that viscosity and solids content of the foaming resins increased with an increase in F/P; the hydroxymethyl index of the resin first increased and then decreased with an increase in F/P, reaching its maximum at F/P = 1.6; the trimer, tetramer, and pentamer contents of the resins increased with an increase in F/P. Nuclear magnetic resonance (¹³C NMR) spectral analysis indicated that the presence of para/para‐methylene, para‐hydroxymethyl, and ortho‐hydroxymethyl groups in the resin gradually increased with an increase in F/P; the proportions of ortho/ortho‐ and ortho/para‐methylene bonds of the resin increased as F/P was increased. The increase in F/P was demonstrated to be conducive to improving the compression strength, thermal stability, and flame retardancy of the phenolic foam and reducing its peak heat release rate and total smoke release. The morphology of phenolic foams show that the closed cell content in the PF foam increases with the F/P ratio until it reaches a ratio of 1.6. Furthermore, the cell size becomes more uniform. POLYM. COMPOS., 36:1531–1540, 2015. © 2014 Society of Plastics Engineers     

13C‐NMR study on cure‐accelerated phenol‐formaldehyde resins with carbonates

Both liquid‐ and solid‐state carbon‐13–nuclear magnetic resonance (¹³C‐NMR) spectroscopies were used to investigate the cure acceleration effects of three carbonates (propylene carbonate, sodium carbonate, and potassium carbonate) on liquid and cured phenol‐formaldehyde (PF) resins. The liquid‐phase ¹³C‐NMR spectra showed that the cure acceleration mechanism in the propylene carbonate‐added PF resin seemed to be involved in increasing reactivity of the phenol rings, whereas the addition of both sodium carbonate and potassium carbonate into PF resin apparently resulted in the presence of ortho–ortho methylene linkages. Proton spin‐lattice rotating frame relaxation time (T_1ρH) measured by solid‐state ¹³C cross polarization/magic‐angle spinning NMR spectroscopy was smaller for the cure‐accelerated PF resins than that of the control PF resin. The result indicated that the cure‐accelerated PF resins are less rigid than the control PF resin. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1284–1293, 2000     

13C‐NMR study on cure‐accelerated phenol–formaldehyde resins with carbonates

Both liquid‐ and solid‐state ¹³C‐NMR spectroscopies were employed to investigate the cure‐acceleration effects of three carbonates [propylene carbonate (PC), sodium carbonate (NC), and potassium carbonate (KC)] on liquid and cured phenol–formaldehyde (PF) resins. The liquid‐phase ¹³C‐NMR spectra showed that the cure‐acceleration mechanism in the PC‐added PF resin seemed to be involved in increasing reactivity of the phenol rings, while the addition of both NC and KC into PF resin apparently resulted in the presence of ortho–ortho methylene linkages. Proton spin‐lattice rotating frame relaxation time (T_1ρH) measured by solid‐state ¹³C‐CP/MAS‐NMR spectroscopy was smaller for the cure‐accelerated PF resins than for that of the control PF resin. The result indicated that cure‐accelerated PF resins are less rigid than the control PF resin. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 841–851, 2000     

Studies on novel binary accelerator system in sulfur vulcanization of natural rubber

The synergistic activity of binary accelerator systems in rubber vulcanization is well known. Binary accelerator systems are being widely used in industry and are becoming increasingly popular because of the fact that such mixed systems can effectively prevent prevulcanization, permit the vulcanization to be carried out at a lower temperature in a shorter time, and produce a vulcanizate with superior mechanical properties compared to those of a stock cured with a single accelerator. Thiourea and its derivatives are important secondary accelerators in this context. It is suggested that thiourea containing binary accelerator systems cause rubber vulcanization to proceed by a nucleophilic reaction mechanism. In the present study 1‐phenyl‐5‐ortho, ‐meta, and ‐para‐tolyl derivatives of 2,4‐dithiobiurets, which are more nucleophilic than thiourea and vary in their nucleophilic reactivity, are used as secondary accelerators along with 2‐morpholinothiobenzothiazole in the vulcanization of natural rubber. The results show an appreciable reduction in the cure time for the mixes containing the dithiobiurets compared to the reference mix. These results are indicative of a nucleophilic reaction mechanism in the vulcanization reaction under consideration. These vulcanizates also demonstrate comparatively better tensile properties and good retention of these properties after aging. An attempt is also made to correlate the variation in physical properties to chemical crosslink formation in the various vulcanizates. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3173–3182, 2003     

Curing properties of high-Ortho phenol-formaldehyde resins with co-catalysis

In this study, sodium carbonate (Na₂CO₃) was used as a catalyst to prepare high-ortho phenol-formaldehyde (HOPF) resin, and ester and carbonate curing accelerators were used to increase its curing rate. The physicochemical properties of the prepared resins and the mechanism of curing acceleration were investigated. The results showed that, with the addition of Na₂CO₃, the ortho/para ratio of methylol groups increased from 7.257 to 27.800. The gel time of the cure-accelerated HOPF resins decreased from 620 to 240 s as compared with PF resin. The bonding strength of plywood bonded with the cure-accelerated HOPF resins were all above 0.70 MPa. The curing acceleration was caused by the carbonate ions rather than the metal ions, and a temporary incorporation mechanism apparently occurred for the ester accelerators. The prepared phenolic resin had fast curing rate, low curing temperature, high thermal stability, and favorable mechanical performance, which has potential for industry applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47229.     

Antineoplastic Isoflavonoids Derived from Intermediate ortho‐Quinone Methides Generated from Mannich Bases

The regioselective condensations of various 7‐hydroxyisoflavonoids with bis(N,N‐dimethylamino)methane in a Mannich reaction provided C‐8 N,N‐dimethylaminomethyl‐substituted isoflavonoids in good yield. Similar condensations of 7‐hydroxy‐8‐methylisoflavonoids led to the C‐6‐substituted analogs. Thermal eliminations of dimethylamine from these C‐6 or C‐8 N,N‐dimethylaminomethyl‐substituted isoflavonoids generated ortho‐quinone methide intermediates within isoflavonoid frameworks for the first time. Despite other potential competing outcomes, these ortho‐quinone methide intermediates trapped dienophiles including 2,3‐dihydrofuran, 3,4‐dihydro‐2H‐pyran, 3‐(N,N‐dimethylamino)‐5,5‐dimethyl‐2‐cyclohexen‐1‐one, 1‐morpholinocyclopentene, and 1‐morpholinocyclohexene to give various inverse electron‐demand Diels–Alder adducts. Several adducts derived from 8‐N,N‐dimethylaminomethyl‐substituted isoflavonoids displayed good activity in the 1–10 μm concentration range in an in vitro proliferation assay using the PC‐3 prostate cancer cell line.     

Catalytic and ortho-directing effect of Zn2+, Mg2+, Ba2+, and Ca2+ metal hydroxides on the preparation of phenolic-formaldehyde resin

A one step method was employed to prepare PF (phenol-formaldehyde) resin adhesive from phenol and formaldehyde with Zn²⁺, Mg²⁺, Ba²⁺, and Ca²⁺ hydroxides as catalysts, and the physicochemical properties of the resulting polymeric material were analyzed. The viscosity of the liquid adhesive decreased at intermediate catalyst concentrations, while the polymerization rate decreased at the highest concentrations; no clear pattern could be observed between catalyst concentration and solid content. Differential scanning calorimetry (DSC) performed on the PF resin catalyzed by Ba²⁺ showed that the polymer had a curing exothermic peak at around 110?°C, while the initial curing temperatures of PF resins were affected by the type of metal hydroxide used, and were in the order Ca²⁺?<?Mg²⁺ <control sample. FTIR spectroscopy was used to monitor the degree of ortho/para substitution during the synthesis of PF resin with Ba²⁺, Ca²⁺, and Mg²⁺ hydroxides. The highest ortho/para ratio was achieved with Ba²⁺ at a concentration of 0.45?wt.%, which also resulted in the most significant increase in the polymerization rate for the formation of PF resin.     

Cure Characteristics of Phenol-Formaldehyde Resin Catalyzed with Ba(OH)2

Phenol-formaldehyde resins are high performance wood adhesives, and are also used to impregnate base papers which are manufactured high-pressure laminates applied in furniture and interior decoration. In this investigation, PF resins catalyzed with Ba(OH)₂ were studied. Both Ba(OH)₂ content and F/P molar ratio were found to influence the cure rate. The cure rate of the Ba(OH)₂ catalyzed PF resin was faster by 50% than that of ordinary PF resin at 150°C. The DSC results showed that the Ba(OH)₂ catalyzed PF resin was cured at a lower temperature than the ordinary PF resin. And the IR results showed that the Ba(OH)₂ catalyzed PF resin has higher degree of ortho-position coupling.     

Structure of polycondensates from hydroxymethylphenols

The structure of oligomers obtained from mono‐hydroxymethylphenols in melt condensation at 120°C was determined using ¹³C NMR spectra in CD₃OD solution. Alongside of methylene region of spectrum, valuable information was obtained from signals of aromatic carbons. Noncatalytic conditions promote the formation of dihydroxydibenzyl ethers in equilibrium with ortho‐ and para‐benzoquinones of oxymethylene derivatives. The final methylene linked oligomers are formed, mainly, by splitting the ether intermediates with free aromatic positions. In alkaline conditions, highly nucleophilic phenoxide ions of ortho‐hydroxymethyl compounds are responsible for substitution in free aromatic positions. The most favored reaction in the mixture of both hydroxymethylphenols is the formation of p,p′‐methylene. In condensation of para‐hydroxymethylphenol, formation of p,p′‐methylene groups occurs with simultaneous release of formaldehyde. High content of alkali stabilized ortho‐hydroxymethyl groups of fully substituted methylene linked oligomers determines the curing behavior of resol phenol–formaldehyde resins. The role of hemiformals in reactions was insignificant. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Influence of sulfenamide accelerators on cure kinetics and properties of natural rubber foam

The effect of types of sulfenamide accelerator, i.e., 2‐morpholinothiobenzotiazole (MBS), N‐t‐butylbenzothiazole‐2‐sulfenamide (TBBS), and N‐cyclohexyl benzothiazole‐2‐sulfenamide (CBS) on the cure kinetics and properties of natural rubber foam was studied. It has been found that the natural rubber compound with CBS accelerator shows the fastest sulfur vulcanization rate and the lowest activation energy (E_a) because CBS accelerator produces higher level of basicity of amine species than other sulfenamide accelerators, further forming a complex structure with zinc ion as ligand in sulfur vulcanization. Because of the fastest cure rate of CBS accelerator, natural rubber foam with CBS accelerator shows the smallest bubble size and narrowest bubble size distribution. Moreover, it exhibits the lowest cell density, thermal conductivity and thermal expansion coefficient, as well as the highest compression set as a result of fast crosslink reaction. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44822.     

Differential scanning calorimetry of phenol–formaldehyde resols

Differential scanning calorimetry was used on a range of synthesized phenol–formaldehyde (PF) resols to discover relationships between formulation parameters or physical properties of resols, and their thermal behavior during cure. The thermograms showed either one or two exothermic reactions. The lower exothermic peak temperature varied between 98 and 129°C with changes in the free formaldehyde content. This exotherm is caused by the addition of free formaldehyde to phenolic rings. The upper exothermic peak temperature varied from 139 to 151°C, with the higher temperatures occurring when the formaldehyde-to-phenol molar ratio was low or the total amount of sodium hydroxide relative to phenol was high. These two factors led to resins which contain a somewhat higher level of unreacted ortho or para aromatic ring positions and no free formaldehyde. Consequently, condensation is probably not solely by the faster self-condensation through hydroxymethyl groups, but also includes the slower condensation of hydroxymethyl groups with unreacted ring positions. Gel times show trends with changes of formulation parameters somewhat similar to trends of the upper exothermic peak temperatures.     

Highly Stereoselective Synthesis of Novel Multistereogenic Bis‐Bifunctional Ligands Based on [2.2]Paracyclophane‐ 4,7‐quinone,their Structure Elucidation and Application in Asymmetric Catalysis

Bis‐bifunctional cis‐4,7‐diarylsubstituted‐4,7‐dihydroxy‐4,7‐dihydro[2.2]paracyclophanes 3–6 were synthesized by a highly diastereoselective reaction of ortho‐substituted aryllithium reagents with [2.2]paracyclophane‐4,7‐quinone ( 1 ). Enantiomerically pure diols 3–5 were tested as chiral inductors in the enantioselective addition of diethylzinc to benzaldehyde (up to 93.5% ee). Acid dehydration of cis‐4,7‐di(2‐methoxyphenyl)‐4,7‐dihydroxy‐4,7‐dihydro[2.2]paracyclophane ( 3 ) results in 4,7‐dihydro‐7,8‐di(2‐methoxyphenyl)[2.2]paracyclophane‐4‐one ( 8 ) – a planar chiral cyclohexadienone of the [2.2]paracyclophane series with a para‐semiquinoid substructure. X‐Ray investigations of compounds 3, 4 and 8 were performed.     

The Metabolic Fate of ortho-Quinones Derived from Catecholamine Metabolites

ortho-Quinones are produced in vivo through the oxidation of catecholic substrates by enzymes such as tyrosinase or by transition metal ions. Neuromelanin, a dark pigment present in the substantia nigra and locus coeruleus of the brain, is produced from dopamine (DA) and norepinephrine (NE) via an interaction with cysteine, but it also incorporates their alcoholic and acidic metabolites. In this study we examined the metabolic fate of ortho-quinones derived from the catecholamine metabolites, 3,4-dihydroxyphenylethanol (DOPE), 3,4-dihydroxyphenylethylene glycol (DOPEG), 3,4-dihydroxyphenylacetic acid (DOPAC) and 3,4-dihydroxyphenylmandelic acid (DOMA). The oxidation of catecholic substrates by mushroom tyrosinase was followed by UV-visible spectrophotometry. HPLC analysis after reduction with NaBH₄ or ascorbic acid enabled measurement of the half-lives of ortho-quinones and the identification of their reaction products. Spectrophotometric examination showed that the ortho-quinones initially formed underwent extensive degradation at pH 6.8. HPLC analysis showed that DOPE-quinone and DOPEG-quinone degraded with half-lives of 15 and 30 min at pH 6.8, respectively, and >100 min at pH 5.3. The major product from DOPE-quinone was DOPEG which was produced through the addition of a water molecule to the quinone methide intermediate. DOPEG-quinone yielded a ketone, 2-oxo-DOPE, through the quinone methide intermediate. DOPAC-quinone and DOMA-quinone degraded immediately with decarboxylation of the ortho-quinone intermediates to form 3,4-dihydroxybenzylalcohol (DHBAlc) and 3,4-dihydroxybenzaldehyde (DHBAld), respectively. DHBAlc-quinone was converted to DHBAld with a half-life of 9 min, while DHBAld-quinone degraded rapidly with a half-life of 3 min. This study confirmed the fact that ortho-quinones from DOPE, DOPEG, DOPAC and DOMA are converted to quinone methide tautomers as common intermediates, through proton rearrangement or decarboxylation. The unstable quinone methides afford stable alcoholic or carbonyl products.     

Cure kinetics of aqueous phenol–formaldehyde resins used for oriented strandboard manufacturing: Analytical technique

The cure kinetics of commercial phenol–formaldehyde (PF), used as oriented strandboard face and core resins, were studied using isothermal and dynamic differential scanning calorimetry (DSC). The cure of the face resin completely followed an nth‐order reaction mechanism. The reaction order was nearly 1 with activation energy of 79.29 kJ mol^?1. The core resin showed a more complicated cure mechanism, including both nth‐order and autocatalytic reactions. The nth‐order part, with reaction order of 2.38, began at lower temperatures, but the reaction rate of the autocatalytic part increased much faster with increase in curing temperature. The total reaction order for the autocatalytic part was about 5. Cure kinetic models, for both face and core resins, were developed. It is shown that the models fitted experimental data well, and that the isothermal DSC was much more reliable than the dynamic DSC in studying the cure kinetics. Furthermore, the relationships among cure reaction conversion (curing degree), cure temperature, and cure time were predicted for both resin systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1642–1650, 2006     

Curing behavior of epoxy resin having hydroxymethyl group

A new type of epoxy resin having hydroxymethyl group was synthesized. This epoxy resin was mixed with commercial epoxy resin in various ratios. The mixed epoxy resins were cured with a mixture of 4,4′-diaminodiphenylmethane and m-phenylenediamine (molar ratio, 6 : 4) as a hardener. Curing behavior of the epoxy resin systems with the hardener was examined by DSC and TG-DSC, and parameters of cure reaction were obtained. Viscoelastic properties of cured resin were studied by dynamic mechanical analyzer. It was found that the higher the amount of epoxy resin having hydroxymethyl group, the lower the activation energy (Ea) and the higher the rate constant (k) were. It was also found that the higher the amount of the epoxy resin having hydroxymethyl group, the better heat resistance the fully-cured resin had. These results were explained as follows: Hydroxymethyl group accelerated an epoxideamine reaction. The crosslinking density of the cured resin was increased because in the hydroxymethyl group occurred a condensation reaction above 200°C.     

Boron-modified phenolic resins for high performance applications

A boron-modified phenolic resin (BPR) that flows at usable processing temperatures was prepared from the solvent-less reaction of triphenyl borate (TPB) and paraformaldehyde (PF). The reaction of TPB and PF was performed at three different resinifying temperatures, 130, 120 and 90 °C. The BPR produced at 90 °C melted upon reheating, which indicated promising processing applications for this resin. ¹H and ¹³C NMR spectra of resins from the three resinifying temperatures had the same pattern of absorptions. Substitution of methylol groups occurred at the ortho and para positions of the ester phenyl rings (4.86-4.75 ppm). Aromatic, methylene and ether linkage protons were assigned at about 7.45-6.74, 4.93-3.36 and 5.30-4.91 ppm, respectively. The synthesis of BPR from the reaction phenolic resins, produced under basic conditions (resoles) and boric acid was not feasible. The reactivity of the resoles species with each other is more favorable than that with boric acid.     

Optimization of accelerators on curing characteristics,tensile, and dynamic mechanical properties of (natural rubber)/(recycled ethylene‐propylene‐diene‐monomer) blends

The migration of sulfur from natural rubber (NR) compound to the ground waste ethylene‐propylene‐diene monomer (EPDM) rubber phase may have caused the cure incompatibility between these two rubbers. Optimization of accelerators had been adopted to overcome the cure incompatibility in NR/(R‐EPDM) blends as well as to get increased curative distribution. In this study, blends of NR and R‐EPDM were prepared. The effect of accelerator type on curing characteristics, tensile properties, and dynamic mechanical properties of 70/30/NR/(R‐EPDM) blend was investigated. Four types of commercial accelerators were selected [ie, N‐tert‐butyl‐2‐benzothiazyl‐sulphonamide , N‐cyclohexyl‐benzothiazyl‐sulfenamide (CBS), tetramethylthiuram disulfide, and 2‐mercaptobenzothiazol]. It was found that the tensile strength of the blends cured in the presence of CBS was relatively higher than the other three accelerators. Scanning electron micrographs of CBS‐cured NR/(R‐EPDM) blends exhibited more roughness and cracking path, indicating that higher energy was required toward the fractured surface. The high crosslinking density observed from the swelling method could be verified from the storage modulus (E′) and damping factor (tan δ) where (tetramethylthiuram disulfide)‐cured NR/(R‐EPDM) blends provided a predominant degree of crosslinking followed by N‐tert‐butyl‐2‐benzothiazyl‐sulphonamide , CBS, and 2‐mercaptobenzothiazol, respectively. J. VINYL ADDIT. TECHNOL., 21:79–88, 2015. © 2014 Society of Plastics Engineers     

Curing partially brominated poly(isobutylene‐co‐4‐methylstyrene) elastomers with phenolic resins: Mechanistic investigation

The crosslinking of partially brominated poly(isobutylene‐co‐4‐methylstyrene) elastomer 1 by phenolic resin crosslinkers was investigated. The curing was modeled using small molecule analogs of the elastomer and the phenolic resin. In order to mimic the conditions that prevail within the highly aliphatic rubber, the study was carried out in isooctane using catalysts such as coated ZnO that are compatible with such low polar media. In situ NMR analysis was used to probe the reaction between the molecular analogs. p‐Isopropyl benzyl bromide was used as the elastomer analog and hydroxymethyl phenols were used as the resin analogs. Isotopic labeling allowed for independent yet simultaneous monitoring of the reactivity of the elastomer and resin analogs. The resin analog reacted with the elastomer analog via an electrophilic aromatic substitution, leading to the formation of a dibenzyl type ether and benzyl‐phenyl type ethers as reaction intermediates. At lower temperatures the elastomer analog reacted with itself in a competing “self‐cure” process that may be suppressed by increasing the homogeneity of the reaction mixture or by increasing the temperature of the reaction. The applicability of the mechanism was confirmed by successful model cure experiments involving a low molecular weight sample of elastomer 1 and the phenolic resin analog. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 680–685, 2001     

Crosslinking reaction mechanism of diisopropyl xanthogen polysulfide accelerator in bromobutyl elastomer for medical device applications

The use of an accelerator based on diisopropyl xanthogen polysulfide (DIXP) to formulate bromobutyl elastomer (BIIR‐DIXP) compositions for sealing medical devices was published in the Journal of Applied Polymer Science (Ohbi, D. S.; Pureval, T. S.; Shah, T.; Siores, E. 2007, 106, 526). In this publication, a reaction scheme for the DIXP accelerator in situ with BIIR is proposed. It is based on the evolved volatile chemical species determined during the curing reaction of BIIR‐DIXP composition, and is formulated in the light of generally accepted mechanism of crosslinking elastomers using sulfur‐based accelerators. The volatile chemical species were determined using coupled thermogravimetric infrared analysis ( TGA‐IR) and head space gas chromatography mass spectroscopy (GC‐MS) analysis. The main volatiles evolved during the curing reaction were carbonyl sulfide, carbon disulfide, and isopropyl bromide. These are considered to be associated with the formation of the active rubber‐bound DIXP sulfurating species required for the crosslinking reaction. Analysis of the acetone extract of cured BIIR‐DIXP also showed that the DIXP is totally consumed during the cure reaction, and the formulation is largely free of cure reaction byproducts. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

13C Nuclear Magnetic Resonance Studies of Phenol-Formaldehyde Resins and Related Model Compounds 2 - Analysis of Sequence Structure in Resins

The paper reports ¹³C nuclear magnetic resonance spectra of novolac resins and the variation of the composition of the reaction mixture during the in situ preparation of resin. It is observed that in the initial stages of the reaction ortho substitution occurs; however the hemiacetal rather than the methylol derivative is observed. These methylol substituted intermediates are highly unstable and a better appreciation of the relative rates of structure formation can be obtained from an analysis of the methylene bridge region, para-para Bridges are the first to appear, the next are the ortho-para and finally the ortho-ortho linkages are observed. Analysis of the relative intensities of ortho and para bridge carbon atoms allows identification of the isomeric composition of the final resin. The proportion of each isomer depends on the catalyst used in synthesis of the resin.