Phenolic and tannin-based adhesive resins by reactions of coordinated metal ligands. II. Tannin adhesive preparation,characteristics, and application

The accelerating effect due to bivalent metal ions observed in simple phenol–formaldehyde reactions are also observed in tannin–formaldehyde resins. Tannin steric hindrance prevents the retarding effect of trivalent metallic ions on tannin–formaldehyde reactions. Small amounts of metal ions do not significantly increase flavonoid B-ring participation to the crosslinking of tannin–formaldehyde networks. Improved plywood strength and shorter pressing times are obtained by the addition of metal ions to tannin/formaldehyde resins. These results are due to faster curing promoted by the presence of the metal ions.     

Resacetophenone-formaldehyde resins,I. Metal chelates

Synthesis and properties of a resacetophenone-formaldehyde resin are described. The number average molecular weight of the resin determined by vapour pressure osmometry and nonaqueous conductometric titration is 2500 and 2200 g/mol, respectively. Cu(II), Ni(II) and Co(II) chelates of the resin were prepared. The elemental analysis of chelates indicated a metal to ligand ratio 1:2. From the diffuse reflectance spectra of the chelates it could be concluded that Ni(II) and Co(II) chelates have a tetrahedral structure while Cu(II) chelate has a square planar structure. Infrared spectral studies showed that the metals are co-ordinated through the oxygen of the carbonyl and phenolic groups. The presence of methylene bridges was also indicated from IR spectral studies. The thermal properties of the resin and its metal chelates are discussed.     

Polyquinoxalines. I. Synthesis and preliminary mechanical properties as laminating and adhesive resins

A study on polyquinoxaline synthesis was conducted which provided a method of obtaining processable, reproducible high molecular weight polymers as solutions in m-cresol; these solutions had excellent storageability at ambient temperatures. Polyquinoxaline solutions in m-cresol were readily used for prepreg and tape preparation. Laminate and adhesive data showed the excellent potential of the polyquinoxalines for high temperature applications.     

Phenolic triazine (PT) resins. I. Gelation phenomenon studied by calorimetric,mechanical, and dielectric techniques

Gelation phenomenon in thermoset polymers is an area of extreme importance from the processing point of view. Gel point (GP) has traditionally been detected using rheological and mechanical techniques. We wish to report the use of dielectric and especially calorimetric techniques for detecting GP. Using a particular thermoset system, we have compared the calorimetric, dielectric, and mechanical techniques and shown how to define GP in terms of time and temperature. As a matter of convenience, we have briefly defined the gelation phenomenon in thermosets, its significance and measurement, and a critical evaluation of the techniques for detecting GP.     

Tannin-based adhesive cross-linked by furfuryl alcohol-glyoxal and epoxy resins

To prepare a natural tannin-based adhesive with good water resistance, an environment friendly furfuryl alcohol-glyoxal resin (FG) synthesized in the laboratory was developed as a cross-linker for tannin-based adhesives. ¹³C Nuclear Magnetic Resonance (NMR) and Matrix-Assisted Laser Desorption-Ionization Time-of-Flight (MALDI-TOF) mass spectroscopy results indicated that furfuryl alcohol and glyoxal reacted under acidic conditions and that the -CH-(OH)- groups could be shown to be the ones involved in the cross-linking of the tannin-furfuryl-glyoxal adhesive (TFG). The results for the wet shear strength of TFG-bonded plywood showed that the cured TFG was improved and better than that bonded with a tannin-furfuryl alcohol (TF) adhesive. Moreover, the TFG adhesive cross-linked with 12% epoxy resin (EPR) presented a good water resistance. It had a modulus of elasticity (MOE) higher than that of tannin-furfuryl alcohol-formaldehyde (TFF), TF and phenol-formaldehyde (PF) adhesives.     

Dynamic mechanical properties and adhesive strengths of epoxy resins modified with liquid rubber. I. Modification with ATBN

The dynamic mechanical properties and the adhesive strengths of Epikote 828 and Epikote 828-ATBN blend systems were investigated. The ATBN blend systems were proved to be completely incompatible with the dynamic mechanical measurement and also fitted well with Takayanagi's model which was designed for completely incompatible two-phase systems. The epoxy resin had a nonreacted part when cured at room temperature. The blending of ATBN reduced the nonreacted part of the epoxy resin, and made contributions to the adhesive strengths. In the case of tensile test of crosslap specimens using aluminium as adherends, the adhesive strengths of ATBN blend systems were almost 1.5-fold of those of epoxy resin without blending of ATBN. As for wood adherends, the maximum of the adhesive strengths was found at 60°C for epoxy resin without blending of ATBN, and at 0°C for ATBN blend systems. The facts meant that there were mutual interactions between the adhesive strengths and the viscoelastic behavior of the adhesive polymers in the two-phase systems as observed in completely miscible polymer blends. There was not pronounced distinction between epoxy resins without blending of ATBN and ATBN blend system, as to the shear adhesive strengths.     

Production of macroporous resins for heavy‐metal removal. I. Nonfunctionalized polymers

The aim of this work was the synthesis of macroporous resins with large specific surface areas through the use of organic solvents (known as porogens or pore‐forming agents) for applications in hexavalent chromium (Cr⁺⁶) removal operations. The synthesis of these materials by suspension polymerization allowed the generation of macroporous structures. The comonomers 4‐vinylpyridine and divinylbenzene were considered in different ratios. Poly(vinyl alcohol) was used as a suspension agent in a mixture of toluene and hexane. The materials produced were characterized with Fourier transform infrared spectroscopy, elemental analysis, thermogravimetry, nitrogen adsorption, and scanning electron microscopy. The macroporous resin with the largest surface area (130 m²/g) was thermally stable up to 300°C and had a structure that included spherical domains with a mean diameter of 68 μm, uniform porosity, and expected high sorption capability. The sorption properties of the resins were evaluated for applications in water‐treatment operations to eliminate Cr⁺⁶ ions at a pH near 7. The advantages of these materials were their high removal capability, high selectivity, and fast adsorption kinetics at a pH 6.5. An aqueous solution of 4 ppm K₂Cr₂O₇ was used to quantify the Cr⁺⁶ content by ultraviolet–visible spectroscopy. A remarkable sorption level (94%) of chromate ions (Cr⁺⁶) was obtained during a 15‐h period for the resin with the highest pyridine group content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Cure of polyester resins. I

The application of physical test methods to studying the crosslinking of unsaturated polyesters is reviewed. Experimental work on changes of hardness and electrical resistivity is described and it is shown that these are not mutually related, due to continual mobility of ionic conditions after the resin network is immobilized by gelation.     

Functionalized allyl resins. I. Photosensitivity of partially cinnamoylated allyl resins

The preparation of photosensitive allyl resins is described. The introduction of cinnamoyl groups into allyl resins is attempted for imparting successfully photosensitive functionality. Thus, the photosensitivity of cinnamoylated poly(allyl benzoate) was first examined in detail as a model photoreaction of cinnamoylated allyl resins. Cinnamoylated poly(diallyl phthalate) was then UV-irradiated to yield crosslinked resin, and its photosensitivity was compared with that of other allyl resins. The highest photosensitivity was observed for cinnamoylated poly(diallyl phthalate), although the mobility of the main polymer chain was considered to be lowest; this may be ascribed to the function of phthaloyl groups as photosensitizers.     

Polymerization of epoxy resins initiated by metal complexes

BACKGROUND: Processing parameters and material properties of epoxy resins can be vastly influenced by choice of curing agent. In this work, metal complexes were investigated as initiators for anionic and cationic epoxide polymerization. Systems for thermally induced and electron beam‐induced curing are described. RESULTS: Zinc or cobalt imidazole complexes of the type [M(imidazole)₂(anion)₂] are efficient initiators for anionic polymerization of glycidyl‐based epoxy resins. The complexes can be employed to prepare tailored resin systems ranging from fast curing systems at slightly elevated temperatures to systems with very high thermal latencies curable at temperatures far above 150 °C. Silver complexes [Ag(L)_n]SbF₆ (L = crown ether or alkene) are highly efficient initiators for cationic curing and low initiator contents of around 1% are sufficient to reach high degrees of crosslinking. The complexes are excellent initiators for both thermally induced and electron beam‐induced polymerizations. CONCLUSION: Metal complexes are powerful initiators for the homopolymerization of epoxy resins and can be designed not only for anionic and cationic polymerization but also for thermal and radiation curing. Based on this study and additional work, a library can be compiled which allows retrieval of optimized metal–ligand–anion combinations and adjustment of the initiators to the respective processing and material demands. Copyright © 2009 Society of Chemical Industry     

Phenolic resins for peptide synthesis. Synthesis of p-hydroxystyrene polymers from p-methoxystyrene

Beaded copolymers of styrene, p-methoxystyrene, and divinylbenzene were obtained by suspension copolymerization of various mixtures of the monomers. Reaction of the polymers with boron tribromide in dichloromethane, followed by methanolysis in carbon tetrachloride, provided a simple and general route to p-hydroxystyrene polymers.     

Polymers containing metal chelate units. I. Immobilized mono- and binuclear chelates of nickel(II) and cobalt(II)

A number of polymer carriers with chelating groups such as diketones, diacylamines, and enaminoketones has been synthesized. The immobilized mono- and binuclear chelates have been prepared by the interaction of these polymeric ligands with nickel(II) and cobalt(II) acetates in alcohol. Spectral and magnetic data confirm the tetrahedral structure of the cobalt complexes and octahedral structure of the nickel complexes. The catalytic properties of the immobilized complexes in ethylene dimerization and butadiene polymerization have been investigated.     

Co-condensates of resorcinols and methylol compounds for adhesive resins

A proton magnetic nuclear resonance study was performed on co-condensation reactions of resorcinol, 5-methylresorcinol and 2,5-dimethylresorcinol with methylol compounds, including ortho- and para-methylolphenol, N-methylol-caprolactam, methylol-N,N-diethylurea, methylolurea and N,N′-dimethylolurea. Spectral assignments, reaction kinetics and composition of products are discussed. The reaction in melt (120°C) with methylolphenols occurs as co-condensation in the presence of all catalysts studied. In resorcinols C4C6 substitution is favored. The rate constants of methylol disappearance clearly indicate the preferable influence of acid and alkaline catalyst (not zinc acetate) on para-methylol. The reaction with N-containing methylol compound does not give any co-condensate in the presence of alkaline catalyst. The optimum conditions for co-condensation mainly depend on reactivity of co-reagents with formaldehyde and stability of methylol compound. The quantitative amount of co-condensate with methylolcaprolactam can be obtained in melt-condensation (70°C) in the presence of acid catalyst. Because of the higher reactivity of urea, the reaction in melt (100°C) in the presence of acid catalyst does not lead to quantitative co-condensation. The condensation of methylol compound or resorcinols with formaldehyde can be avoided substantially by performing the reaction in aqueous solution at lower temperature.     

Melt fracture behavior of polypropylene‐type resins with narrow molecular weight distribution. II. Suppression of sharkskin by addition of adhesive resins

Standing on a hypothesis that the sharkskin of a polymer with a narrow molecular weight distribution at extrusion processing originates from a stick‐slip of the polymer at the die wall, the suppression of the sharkskin was tried by means of suppressing the slip by the addition of adhesives. To polypropylene (PP)‐type resins with narrow molecular weight distributions such as a PP‐type thermoplastic elastomer, PER and a controlled rheology PP were added small amounts of adhesives such as maleated PP, maleated PER, reactive polyolefin oligomers, ethylene/ethylacrylate/maleic anhydride (MAH) copolymer, ethylene/vinyl acetate copolymer, and styrene/MAH copolymer, and their melt fracture behaviors at capillary extrusion were observed. It was found that the sharkskin of the PP‐type resins with narrow molecular weight distributions was suppressed by the addition of the adhesive resins with good adhesion to metal. The suppressive effect of the sharkskin was generally the more remarkable by the higher loading of the adhesives with the higher MAH content. This is the direction of increasing adhesion. From this fact, it was assumed that the sharkskin of the PP‐type resins with narrow molecular weight distribution does not originate from a periodic growth and relaxation of tensile stress at the extrudate surface but from a stick‐slip at the die wall. Based on this mechanism, it may be said that the sharkskin can be suppressed by both ways of directions of promoting and suppressing the slip at the die wall. The former way is the previously known method, and the latter way is the method proposed in the present study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2120–2127, 2002     

Curing reactions and modeling of silicone-carbon resins

New silicone-carbon resins have been made, based on four- or five-membered cyclosiloxanes, cyclopentadiene dimer (DCPD), and cyclopentadiene trimer (TCPD). The monomers are first polymerized to a B-stage resin, and then heated at higher temperatures to cure. In this work, the curing reaction of this silicone-carbon resin (which leads to network formation) is simulated using two approaches. In the first approach (stochastic model), all the available functional groups (olefin and silyl hydride) are allowed to react with each other with equal probability. This gives the kinetically controlled, liquidlike, diffusion-free limit. Extrapolation of the model to reactions where diffusion may play a role can be made by including molecular weight dependence in the rates. This dependence on the molecular weight can be scaled to fit the experimental data. In the second approach a percolation model is used. In the extreme case, this model corresponds to the solid-state reaction between silicone-carbon resin molecules on 2-dimensional or 3-dimensional rigid lattices. Relaxation of this geometric constraint can be made by providing a larger reacting distance between the reactants. Computer programs have been written for 2- and 3-dimensional lattices. Illustrative examples are given for these approaches. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1557–1573, 1997     

Degradation of polycyclic aromatic hydrocarbons by hydrogen peroxide catalyzed by heterogeneous polymeric metal chelates

Chelating sorbents with 8-hydroxyquinoline (IVa), 8-hydroxyquinoline-5-sulfonic acid (IVb), and tris(2-aminoethyl)amine (VI) ligands immobilized on macroporous methacrylate matrix were prepared and saturated with Co(II), Cu(II), and Fe(II). All these chelates catalyze cleavage of H₂O₂ yielding highly reactive hydroxyl radicals. All were able to degrade by this mechanism polycyclic aromatic hydrocarbons (anthracene, benzo[a]pyrene and benzo[k]fluoranthene). The most effective catalysts IVa-Fe, IVb-Fe, and VI-Cu (25 mg with 100 μmol H₂O₂) performed complete decomposition of 33 μg anthracene and benzo[a]pyrene during one 7-day catalytic cycle at 25 °C. The fastest decomposition proceeded during the 1st day of incubation; 75% of anthracene and 74% of benzo[a]pyrene were decomposed by IVb-Co within the first 24 h. More than 25% decomposition within the 1st day was also achieved with IVb-Fe, VI-Cu, IVa-Cu, and VI-Co for anthracene and more than 30% benzo[a]pyrene was decomposed by IVb-Fe, VI-Cu, IVa-Cu, and IVb-Cu during the same period. 1,4-Anthracenedione was the main product of anthracene oxidation by all catalysts. The catalysts were stable at pH 2–11 depending on their structure and able to perform sequential catalytic cycles without regeneration.     

Surface modification of polyethylene by radiation-induced grafting for adhesive bonding. I. Relationship between adhesive bond strength and surface composition

A number of vinyl monomers have been surface grafted onto a polyethylene sheet by the mutual irradiation in monomer vapor and by a trapped-radical technique. The surface composition of the grafted sheets has been determined by means of ATR infrared spectrophotometry and compared with the peel strength of the joints bonded with conventional structural adhesives. In the methyl acrylate grafts followed by a saponification treatment, only the surfaces having graft compositions of more than 80 mole-% methyl acrylate give a high peel strength. A similar relationship between peel strength and surface composition is found in the surface grafts of vinyl acetate, acrylic acid, acrylamide, and methylolacrylamide. It is concluded that the formation of a surface with such a high monomer content is a necessary condition for the strong adhesive bonding of grafted polyethylenes at bonding temperatures below the softening point. Moreover, the adhesive bondability of the highly modified surfaces with epoxy adhesives is significantly enhanced by the introduction of carboxy and carbamyl radicals.     

State-of-the-art production of epoxy resins and adhesive hardeners in Russia

The commercial production of epoxy resin ED-20 is discussed as this resin is the most important component in the formulations of adhesives and sealants in the Russian Federation. Classification of amine hardeners is presented, and basic trade marks of ethylene amines, modified amines, oligoaminoamide and imidazoline hardeners are listed, and their major characteristics are described.