Structural characteristics of phenol formaldehyde novolak resin depending on polycondensation type using molecular simulation

Phenol formaldehyde novolak resins have various structures depending on the polycondensation types. Their structures were characterized using molecular mechanics and molecular dynamics. Dimer, tetramer, hexamer, octamer, and decamer of the resins with the ortho–ortho, ortho–para, and para–para sequences were calculated. The ortho–ortho resins have the structural characteristics of intramolecular hydrogen bonds between hydroxyl groups of the adjacent phenolic units. For the ortho–para and para–para resins, the intramolecular hydrogen bonds are formed mainly between hydroxyl groups of the backbone phenolic units. The para–para resins also have intramolecular hydrogen bonds between hydroxyl groups of the branched phenolic units. A factor determining the structural characteristics of the resins was found to be the geometry of the basic unit (dimer). The order of the end‐to‐end distances between hydrogen atoms on the para‐position of the basic units of the resins is ortho–ortho resin < ortho–para resin < para–para resin. The calculational results were found to be consistent with the gel permeation chromatography (GPC) analysis. Copyright © 2001 John Wiley & Sons, Ltd.     

Chemistry of novolac resins. X. Polymerization studies of HMTA and strategically synthesized model compounds

The reactions between hexamethylenetetramine (HMTA) and compounds which model novolac resins have been studied by ¹³C‐ and ¹⁵N‐NMR techniques. The dimer and tetramer compounds vary in molecular size and structure and react with HMTA to yield benzylamines and benzoxazine as the major initial‐formed intermediates and convert to methylene linked compounds at increased temperatures. The reaction of the compounds with only ortho reactive sites paralleled the 2,4‐xylenol–HMTA case reported by us previously; however, increasing molecular weight favored the formation of benzylamines and not benzoxazines. Those compounds with only para reactive sites paralleled the 2,6‐xylenol–HMTA case. The reactivity of the systems containing both ortho and para reactive sites depends on the ratio of ortho/para sites and various aspects such as the chemical structure and molecular weight of the compound, the HMTA level, and the melting point and pH of the system. These results parallel those obtained from novolac/HMTA systems. The xylenol/HMTA reactions formed similar products but showed quite different relative reaction rates by varying the HMTA ratio and structures of the materials. The importance of careful selection of model systems is also discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1347–1355, 1999     

Epoxy resins from novel monomers with a bis‐(9,10‐dihydro‐9‐oxa‐10‐oxide‐10‐phosphaphenanthrene‐10‐yl‐) substituent

A new diepoxide and a new diamine, both bearing bis‐(9,10‐dihydro‐9‐oxa‐10‐oxide‐10‐phosphaphenanthrene‐10‐yl‐)‐substituted methylene linkages, were prepared through the reaction of 9,10‐dihydro‐oxa‐10‐phosphaphenanthrene‐10‐oxide with benzophenone derivatives via a simple addition reaction followed by a dehydration reaction. These two compounds were used as monomers for preparing cured epoxy resins with high phosphorus contents. The resultant epoxy resins showed high glass‐transition temperatures (between 131 and 196 °C). All of the cured epoxy resins exhibited high thermal stability, with 5% weight loss temperatures over 316 °C, and excellent flame retardancy, with limited oxygen index values of 37–50. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 359–368, 2002     

DNQ–novolac photoresists revisited: 1H and 13C NMR evidence for a novel photoreaction mechanism

Photoactive compounds, such as diazonaphthoquinone (DNQ) esters, blended with novolac resins, solvents and certain additives, serve as photoresists. These are used for printing of electronic circuits at the micron or sub‐micron level. Patterns are generated based on changes in the physical and chemical properties of the exposed and unexposed photoresist surfaces (printed circuit boards). The huge polarity change between the exposed and unexposed photoresists is exploited in the technique of microlithography. It is believed that the large polarity difference is due to acid formation in the exposed photoresist by a photochemical reaction of DNQ on exposure to light. However, it has also been suggested that in the unexposed part of a photoresist, the novolac resin undergoes an azo coupling reaction with DNQ, leading to an increase in the molecular weight of the resin, rendering it more insoluble in base. The protons in the para positions of the m‐cresol units incorporated in the novolac resin are believed to take part in this azo coupling reaction with DNQ. In this paper, we propose a novel mechanism of action of positive photoresists in the unexposed part of photoresists for dissolution inhibition using molecular modelling, ¹H NMR, ¹³C NMR and DEPT‐135 NMR spectroscopic techniques. Our results enable us to propose that the diazo group of DNQ attacks the methylene bridges rather than the aromatic moiety of the resin. This mechanism explains the pattern formation observed using even p‐cresol‐based resins, where no free para positions are present in the aromatic ring. Copyright © 2003 John Wiley & Sons, Ltd.     

The reaction of furfuryl alcohol resins with hexamethylenetetramine: A 13C and 15N high-resolution solid-state NMR study

The reactions between furfuryl alcohol (FA)/poly(furfuryl alcohol) (PFA) and hexamethylenetetramine (HMTA) have been studied by ¹³C and ¹⁵N high-resolution solid-state NMR techniques. Highly crosslinked polymer networks similar to those obtained from the thermal curing of FA resins under acidic condition are formed. Possible reaction pathways are postulated on the basis of changes of chemical structures during the curing; α-substituted furfurylamines are shown to be the initial intermediates. Their further reactions with FA/PFA, together with thermal decomposition, produce methylene linkages between furan rings, resulting in chain extension and crosslinking, which occurs at both the methylene linkages and the 3- or 4-C of furan rings. Various side-products such as amines, imines, amides, imides, and nitriles are also formed during the reactions, and some of these can remain in the resins up to 205°C. The crosslinked network can be heterogeneous with different structures on nanometer scales when higher oligomers of FA resins react with HMTA. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2233–2243, 1997     

Polymers from renewable resources. XXI. Semi-interpenetrating polymer networks based on cardanol-formaldehyde-substituted aromatic compounds copolymerized resins and castor oil polyurethanes: Synthesis,structure, scanning electron microscopy and XRD

Substituted aromatic compounds incorporated–cardanol–formaldehyde novolac resins were synthesized by acid base catalyzed reactions. A number of improved high temperature stable interpenetrating polymer networks (semi-IPNs) were prepared by condensing novolac resins and polyurethanes prepared from castor oil and diisocyanates of varying NCO/OH ratio. The structure of these semi-IPNs were studied using various characterization techniques such as IR, nuclear magnetic resonance (NMR) spectra. The scanning electron microscopy of some of the semi-IPNs have been studied and the morphology has been examined. The samples were subjected to wide angle X-ray diffraction analysis. The degree of crystallinity (X_cr) was computed on the basis of the crystal defect concept, developed by Ruland and Vonk. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3117–3124, 1997     

Adamantyl-substituted phenolic polymers

4-(1-Adamantyl)phenol was synthesized via Friedel-Crafts reaction of 1-bromoadamantane and phenol. Substitution in the phenol para position forces polymerization to occur only in the ortho positions to give a linear polymer. Variations in formaldehyde amount, reaction time, and catalyst were evaluated. Increasing the amount of paraformaldehyde increased formation of cyclic octamer, an easily identified by-product due to its insolubility in common organic solvents. The cyclic octamer was acetylated to give a soluble model compound for comparison to acetylated polymers by IR and NMR. All of the synthetic variations employed produced low molecular weight polymers as indicated by NMR end-group analysis and SEC. The polymers showed number-average molecular weights of ca. 3000 (versus polystyrene standards by SEC), and exhibited glass transition temperatures ranging from 175–230°C, an increase of ca. 100°C over unsubstituted and para-alkyl substituted analogs. All of the samples exhibited a 10% weight loss at 400°C in nitrogen, indicating thermal stability much greater than the parent and alkyl-substituted polymers. © 1996 John Wiley & Sons, Inc.     

Preparation of polymeric alcohol bearing oligo(oxyethylene) moiety by radical polyaddition through ketyl radical

Hydrophilic polymers having both oligo(oxyethylene) moieties and tertiary alcohol units in the main chain were prepared by the radical polyaddition of the dike-tones with distyryl compounds by using samarium(II) iodide as an electron transfer agent. Polyaddition of 4,4′-(1,4-phenylene)bis-2-butanone or 6,9-dioxatetradeca-2,13-dione with distyryl compounds such as 1,15-di(4-ethenylphenyl)-2,5,8,11,14-pentaoxapentadecane, 1,18-di(4-ethenylphenyl)-2,5,8,11,14,17-hexaoxaoctadecane, or 1,21-di(4-ethenylphenyl)-2,5,8,11,14,17,20-heptaoxaheneicosane resulted in the formation of the corresponding polymeric alcohols in moderate yields (46–75%). The produced polymers showed high solubility in common solvents, and their molecular weights estimated by GPC (THF, polystyrene standard) were 5200–8100. No serious difference in the molecular weight of the polymer between after and before the treatment with cerium ammonium nitrate indicated that the produced polymers were inert under the oxidative condition where oxidative cleavage of the main chain of poly(vinyl alcohol) takes place. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 715–720, 1997     

Functional Polymers. VIII. Polyesters from Hindered Bisphenols

It was demonstrated that highly hindered bisphenols could be used to produce polyesters of moderate molecular weight. Bisphenols linked in the 4 and 4′ or the 2 and 2′ positions and substituted in positions ortho and para to the phenolic hydroxyl groups with methyl or tertiary butyl groups (these bisphenols are now used as very effective antioxidants) formed polymers, their reactivity depending more on the nature of the group linking the two phenyl rings than on the steric effects of the ortho substi-tuents. Bisphenols linked in the 2 and 2′ positions and containing bulky electron-withdrawing groups were found to be least effective as condensation monomers although successful polymerization to moderate molecular weight could be achieved using me it polycondensation techniques.     

Structural characteristics of p‐t‐Octylphenol formaldehyde resole resins using molecular simulation

p‐t‐Octylphenol formaldehyde resole resins have two linkage types of methylene‐ and dimethylene ether‐linkages and have three terminal types of hydrogen, methylol, and o‐methylene quinone. Variation of structural characteristics of the resins due to different types of linkages and terminals were studied using molecular dynamics and molecular mechanics. The structural characteristics of the methylene‐bridged resins were intramolecular hydrogen bonds between hydroxyl groups of the adjacent p‐t‐octylphenols. In the dimethylene ether‐bridged resin, the intramolecular hydrogen bonds between oxygen atoms of the dimethylene ether‐linkages and hydroxyl groups of the neighboring phenolic units were found. For the resins with both methylol terminals, one of both terminals of the resins was hidden at the center of the molecule when the resin size is large. The number of hydrogen bonds in the resins with the methylol terminal was larger than for the resins with the o‐methylene quinone terminal. Variation of the structural characteristics of the resins by dehydration of the terminal methylol was discussed. Using the calculated results, dissociation of the dimethylene ether linkage and crosslinking reaction of rubber chains by the resin were explained. Copyright © 2002 John Wiley & Sons, Ltd.     

Keto forms of salicylaldehyde Schiff bases: structural and theoretical aspects

Twelve Schiff bases of methoxy-substituted salicylaldehyde have been examined by crystallographic and spectroscopic methods, as well as by DFT theoretical calculations in order to investigate the effect of the substituent's position on the keto-enol equilibrium in the crystalline state. Four out of the 10 structurally characterized compounds with methoxy substitution on the para and/or ortho positions with respect to the aldimine bridge and deriving from aliphatic amines or alkylarylamines are found as cis-keto tautomers and form dimers. In contrast, the five pure enol tautomers derive either from aliphatic or alkylarylamines and are meta substituted or from aniline or benzylamine and are para and/or ortho methoxy substituted. The DFT calculations support the crystallographic results and, moreover, they have shown that keto and enol tautomers are affected differently by the relative arrangement of the monomers. Overall, the DFT calculations point to a plausible hypothesis for the stabilization of the keto form in the crystalline state: In cases with a sufficiently low enol-keto energy difference of the isolated monomers, as when the methoxy group is at ortho and/or para positions with respect to the aldimino group, extra stabilization of the keto form is derived from molecular association, thus leading to its crystallization.     

Water-soluble ABC triblock copolymers based on vinyl ethers: Synthesis by living cationic polymerization and solution characterization

Water-soluble ABC triblock copolymers of methyl vinyl ether (MVE), ethyl vinyl ether (EVE), and methyl tri(ethylene glycol) vinyl ether (MTEGVE) of various block sequences and carrying 20 monomer units in each block were synthesized by living cationic polymerization. In addition to the triblocks, one AB diblock, one BA diblock, and one statistical copolymer of MVE and MTEGVE carrying 20 units of each type of monomer were synthesized as controls. Moreover, three homopolymers each carrying 20 units of MVE and end groups of varying hydrophobicity were synthesized using three different initiators. The molecular weights and molecular weight distributions of all the polymers were determined by gel permeation chromatography (GPC) in tetrahydrofuran (THF). The number average degrees of polymerization (DP_ns) and composition of all the polymers were calculated by proton nuclear magnetic resonance (¹H-NMR) spectroscopy. The molecular weights and degrees of polymerization corresponded to the values expected from the monomer/initiator ratios. The calculated polydispersities were reasonably narrow at 1.3. Aqueous GPC studies at room temperature on the triblock copolymers showed that the polymers exist as isolated chains (unimers) in solution but they tend to assemble and form micelles in the presence of a sufficiently high salt concentration apparently due to the insolubility of the EVE units under the latter conditions. Triblocks with a different block sequence exhibited a different susceptibility to salt-induced micellization, as indicated by the retention volume of the micelles and the relative micelle/unimer peak areas. Similarly, the cloud points of the triblock copolymers covered a relatively wide temperature range from 56 to 72°C. These differences in micellization and cloud points suggest a profound effect of the location of the hydrophilic MTEGVE block on copolymer association. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1181–1195, 1997     

含磺酰胺基和羧苯基的异方酰胺的合成

以3-[邻(或对)羧苯胺基]-4-羟基-3-环丁烯二酮(1a, 1b)为底物,与一些磺胺反应, 成功地制得了14个新的不对称取代的异方酰胺。3a～3f和4a～4f结构上的共同特点是, 有药物作用的磺酰胺和邻(或对)氨基苯甲酸的结构单元, 通过方酸四碳环的桥接作用而共存于同一分子之中。     

Synthesis,polymerization, and isomerization of isoimide containing acrylate esters

Several isoimides substituted with hydroxylated substituents were prepared, and allowed to react with acryloyl chloride to form the corresponding acrylate esters. The acrylates were polymerized free radically using AIBN as the initiator yielding medium molecular weight polyacrylates. Upon warming the prepared polyacrylates or treatment with base most of the isoimide pending groups rearranged to the stable form of the corresponding imides. These rearrangements were accompanied by increase in softening points of the polymers forming thermally more stable resins. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3125–3130, 1997     

Synthesis of polycarbonates by a silicon-assisted alkoxy/carbonylimidazolide coupling reaction

The investigation of a silicon-mediated coupling reaction between hydroxyl and carbonylimidazolide functional groups in the preparation of carbonate linkages is described. Application of this reaction to the formation of aliphatic polycarbonates was accomplished by the polymerization of an AB monomer unit, which was composed of 1,4-cyclohexanediol, where one of the hydroxyl groups was protected as a dimethylphenylsilyl ether and the other carried the carbonylimidazolide functionality. Reaction of this monomer with cesium fluoride removed the silicon protecting group and the resulting alkoxy anion promoted polymerization. Poly(1,4-cyclohexanecarbonate)s with typical molecular weights of M_w = 20,000 and M_n = 7300 a.m.u. (from GPC based upon polystyrene standards) were prepared in ca. 65% yield. The polymer showed a glass transition temperature at 138°C by DSC. TGA gave 85% mass loss between 275 and 350°C. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1133–1137, 1997.     

Novel flame‐retardant thermosets: Diglycidyl ether of bisphenol A as a curing agent of boron‐containing phenolic resins

Boron‐containing novolac resins were synthesized by the modification of a commercial novolac resin with different contents of bis(benzo‐1,3,2‐dioxaborolanyl)oxide. These novolac resins were crosslinked with diglycidyl ether of bisphenol A (DGEBA), and their thermal, thermodynamomechanical, and flame‐retardant properties were evaluated. The boron‐containing novolac resins were less thermally stable than the unmodified novolac resin. Their modification degree and DGEBA content were related to the crosslinking density of the materials. The boron‐containing novolac resins generated boric acid at high temperatures and gave an intumescent char that slowed down the degradation and prevented it from being total. They also showed good flame‐retardant properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1701–1710, 2006     

Conformationally restricted linear polyurethanes from acetalized sugar‐based monomers

Linear polyurethanes based on sugar monomers having D ‐gluco, galacto, and D ‐manno configurations and their secondary hydroxyl groups protected as bicyclic acetals, have been prepared by polyaddition reaction of these diol monomers to hexamethylene diisocyanate ( HMDI ) and 4,4′‐methylene‐bis(phenyl isocyanate) ( MDI ). The new polyurethanes seem to be amorphous materials, except that obtained from 2,3:4,5‐di‐O‐methylene‐galactitol and HMDI. Weight‐average molecular weights, determined by GPC, were in the range 16,000–115,200. TGA analyses indicated that the thermal stability of these bicyclic polyurethanes is comparable to those based on the isosorbide; both the onset and the maximum rate decomposition temperatures increased significantly with respect to the polyurethanes based on acyclic sugar monomers. The presence of the acetalized alditol units in the polyurethanes also increased the T_gs as compared with their acyclic analogs. Deacetalization of the polyurethanes containing di‐O‐isopropylidene‐D ‐mannitol units yielded the polyhydroxylated polymers in good yields, without apparent degradation of the polymer chain. These hydroxylated polymers showed an enhanced hydrophilicity and degradability and lower T_gs and thermal stability than their parent acetalized polyurethanes. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Analysis of resoles by gel-permeation chromatography

Resoles, the complex, heat-sensitive product mixture from the alkali-catalyzed reactions of phenol with formaldehyde were investigated by gel-permeation chromatography (GPC). The low molecular weight species of these resins which consisted of mono-and dinuclear methylol phenols were resolved into multiple peaks. Model compounds were used to identify the peaks of the specific methylol phenols or methylene etherbridged diphenols. Differences in the refractive index of individual species restricted the quantitative analysis of low molecular weight components in the resole. The effects of sodium and barium hydroxides and hexamethylene-tetramine as catalysts, reaction temperature, and time on the total composition of a resole are demonstrated with the gel-permeation chromatographic spectrum and with the aid of NMR. Formation of a “secondary” resole by methylolation of the bisphenol of formaldehyde was also monitored by GPC.     

Alkyl-substituted poly(2,5-benzophenone)s synthesized via Ni(0)-catalyzed coupling of aromatic dichlorides and their miscible blends

High molecular weight poly(2,5-benzophenone) derivatives were prepared by Ni(0)-catalyzed coupling of 4′-substituted 2,5-dichlorobenzophenones. Monomers were synthesized by the Friedel–Crafts reaction of 2,5-dichlorobenzoyl chloride and alkyl-substituted benzenes in the presence of aluminum chloride. The resulting polymers are soluble and show no evidence of crystallinity by DSC. Number average molecular weights are in the range of 9.2 × 10³–11.7 × 10³ g/mol by multiple angle laser light scattering (MALLS). Molecular weights obtained by MALLS are only slightly lower (∼90%) than those obtained by GPC (polystyrene standards). These polymers exhibit high thermal stability with glass transition temperatures ranging from 173 to 225°C and weight loss occurring above 450°C in nitrogen and 430°C in air. Additionally, the polymers were blended and the resulting polymer films appear to be miscible by DSC results. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2611–2618, 1998     

Development of novel flame‐retardant thermosets based on benzoxazine–phenolic resins and a glycidyl phosphinate

Modified novolac resins with benzoxazine rings were prepared and copolymerized with a glycidyl phosphinate. Their curing behavior and the thermal properties of the curing resins were studied. Copolymerization was studied with model compounds considering the functionality of the benzoxazine‐based phenolic resins and the easy isomerization of the glycidyl phosphinate. Phenolic novolac resin acts as an initiator but p‐toluensulfonic acid had to be used to decrease the curing temperature and to prevent glycidyl phosphinate from isomerizing. The materials obtained exhibited high glass‐transition temperatures and retardation on thermal degradation rates. V‐0 materials were obtained when the materials were tested for ignition resistance with the UL‐94 test. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 279–289, 2004