Phenol-formaldehyde polymers resin preparation

A phenol-formaldehyde polymer resin was carbonized in Nj flow at 1000°C during 1 hour, heating rate of 5°C/min (carbon C-III) and then activated in CO2 at 800°C for 60 hours to reach 32% burn-off (carbon AC-III). Further details of sample preparation and characterization is given elsewhere (ref. 3) for olive stone and (ref. 4) for almond shell and the polymer. 

Polymers. Quinoline and its derivatives may be added to or incorporated in polymers to introduce ion-exchange properties (see Ion exchange). For example, phenol—formaldehyde polymers have been treated with quinoline, quinaldine, or lepidine (81) (see Phenolic resins). Resins with variable basic exchange capacities have been prepared by treating Amherlites with 2-methylquinoline (82). 

When two polymeric systems are mixed together in a solvent and are spin-coated onto a substrate, phase separation sometimes occurs, as described for the application of poly (2-methyl-1-pentene sulfone) as a dissolution inhibitor for a Novolak resin (4). There are two ways to improve the compatibility of polymer mixtures in addition to using a proper solvent modification of one or both components. The miscibility of poly(olefin sulfones) with Novolak resins is reported to be marginal. To improve miscibility, Fahrenholtz and Kwei prepared several alkyl-substituted phenol-formaldehyde Novolak resins (including 2-n-propylphenol, 2-r-butylphenol, 2-sec-butylphenol, and 2-phenylphenol). They discussed the compatibility in terms of increased specific interactions such as formation of hydrogen bonds between unlike polymers and decreased specific interactions by a bulky substituent, and also in terms of "polarity matches" (18). In these studies, 2-ethoxyethyl acetate was used as a solvent (4,18). Formation of charge transfer complexes between the Novolak resins and the poly (olefin sulfones) is also reported (6). 

Another reason for predicting low emissions is that the small amount of residual formaldehyde that might be present in the prepared resin is diminished even farther by reactions which occur when the resin cures. Phenolic resins are cured under heat and pressure in a hot-press, usually under highly alkaline conditions. Curing temperatures are usually in the range of 130-220 C. Under these conditions, unreacted formaldehyde continues to react with phenol to form larger phenol formaldehyde polymers. Also, some formaldehyde reacts with various chemical constituents in the wood. Moreover, some formaldehyde is probably converted to methyl alcohol and formic acid by way of the Cannizzaro reaction (J ). ... 

Euiaiiopsis binata fibers were obtained from the local resources of the Himalayan region. Phenol, formaldehyde solution, and sodium hydroxide of Qualigens make were used as received from their vendors [26-29]. Phenol-formaldehyde [PF] resin to be used as the polymer matrix for the preparation of the composites was prepared using the standard method reported in the literature... 

Fast pyrolysis of biomass produces a phenol-rich oil suitable for incorporation into phenol-formaldehyde (PF) resins. To evaluate the reactivity and network formation characteristics of the compounds typically found in these oils, a series of phenolic model compounds was reacted with formaldehyde under conditions typically used to prepare PF resins. This study indicates that the substituted phenolics commonly found in pyrolysis oils are more reactive than phenol. It also showed that the network formation process for tiiese complex phenolic mixtures follows the predictions of the simple statistical approaches developed by Flory (23) and Stockmayer (24). These results show that the substituted phenolics commonly found in pyrolysis oils will be chemically bonded into the polymer network and that under the proper reaction conditions a highly stable network will be formed. 

There are two types of phenol-formaldehyde condensation polymers resoles and novolacs (117). Phenol-formaldehyde polymers prepared from the base-catalyzed condensation of phenol and excess formaldehyde are called resoles. In most phenolic resins commonly used with epoxies, the phenolic group is converted into an ether to give improved alkali resistance. At elevated temperatin-es (>150°C), resole resins react with the hydroxyl groups of the epoxy resins to provide highly cross-linked polymers. 

In the manufacture of pure resorcinol resins, the reaction can be violently exothermic unless controlled by the addition of alcohols. Because the alcohols perform other useful functions in the glue mix, they are left in the liquid adhesive. PRF adhesives are generally prepared firstly by reaction of phenol with formaldehyde to form a PF resol polymer, that has been proved to be in the greatest percentage, and often completely, linear [95], In the reaction step that follows the resorcinol chemical is added in excess to the PF-resol to react it with the PF-resin -CH2OH groups to form PRF polymers in which the resorcinol groups can be resorcinol chemical or any type of resorcinol-formaldehyde polymer. 

Phenol-formaldehyde resins using prepolymers such as novolaks and resols are widely used in industrial fields. These resins show excellent toughness and thermal-resistant properties, but the general concern over the toxicity of formaldehyde has resulted in limitations on their preparation and use. Therefore, an alternative process for the synthesis of phenolic polymers avoiding the use of formaldehyde is strongly desired. 

In the early 1930 s, a second type of resin prepared from formaldehyde was introduced to the market—namely, urea-formaldehyde resins. A few years later, melamine-formaldehyde resins also appeared. The same basic process is employed in polymerization of all these resins it consists of the catalyzed reaction of formaldehyde with the second ingredient—phenol, urea, or melamine—to evolve water and produce three-dimensional, cross-linked thermosetting polymers. 

Synthetic resins, such as phenolic and cresylic resins (see PHENOLIC RESINS), are the most commonly used friction material binders, and are usually modified with drying oils, elastomer, cardanol [37330-39-5], an epoxy, phosphorus- or boron-based compounds, or even combinations of two. They are prepared by the addition of the appropriate phenol and formaldehyde [50-00-0] in the presence of an acidic or basic catalyst. Polymerization takes place at elevated temperatures. Other resin systems are based on elastomers (see Elastomers, synthetic), drying oils, or combinations of the above or other polymers. 

The mechanical degradation and production of macroradicals can also be performed by mastication of polymers brought into a rubbery state by admixture with monomer several monomer-polymer systems were examined (10, 11). This technique was for instance studied for the cold mastication of natural rubber or butadiene copolymers in the presence of a vinyl monomer (13, 31, 52). The polymerization of methyl methacrylate or styrene during the mastication of natural rubber has yielded copolymers which remain soluble up to complete polymerization vinyl acetate, which could not produce graft copolymers by the chain transfer technique, failed also in this mastication procedure. Block and graft copolymers were also prepared by cross-addition of the macroradicals generated by the cold milling and mastication of mixtures of various elastomers and polymers, such as natural rubber/polymethyl methacrylate (74), natural rubber/butadiene-styrene rubbers (76) and even phenol-formaldehyde resin/nitrile rubber (125). 

Blending of inert materials with ion-exchange resins to an extent that the desirable properties such as thermal stability and exchange capacity are not affected can partially replace the polymer content thereby reducing the production cost. Vasudevan et al. reported the preparation of phenol-formaldehyde composite ion-exchange... 

The earliest polymers of practical use were prepared by step-growth reactions, most notable among them Bakelite, a phenol-formaldehyde copolymer first marketed in 1910 [4]. Its name was long almost synonymous with synthetic plastics and resins, has become generic, and is no longer restricted to phenol-formaldehyde copolymers. Most but not all step-growth polymerizations are condensations. 

Carbonaceous materials (CMs) are sometimes also named polymeric carbons. They are mostly prepared by thermal decomposition of organic precursors. One strategy is pyrolysis of gaseous or vaporized hydrocarbons at the surface of heated substrates, a second is heating (pyrolysis) of natural or synthetic polymers, both in an inert atmosphere. The latter is of special interest, and according to Miyabayashi et al. [374], precursors such as condensed polycyclic hydrocarbons, polymeric heterocyclic compounds, phenol-formaldehyde resins, polyacrylonitrile or polyphenylene are heated to 300-3000 °C for 0.15-20 h. Sometimes, a temperature/time profile is run. The temperature range must be divided into two domains, namely... 

Some of the factors identified in determining the final properties of these resins are the phenol-formaldehyde ratio, pH, temperature and the type of catalyst (acid or alkaline) used in the preparation of the resin. The phenol-formaldehyde ratio (P/F) (or formaldehyde to phenol ratio, F/P) is a most important factor as it leads to two different classes of synthetic polymers, namely Novolacs and resoles. The first class of resins, Novolacs, is produced by the reaction of phenol with formaldehyde with a P/F > 1 usually under acidic conditions (Scheme 2a). Resoles are produced by the reaction of phenol and formaldehyde with a P/F <1 usually under basic conditions (Scheme 2b). 

This entry will provide an overview of the classical phenol-formaldehyde system. The fundamentals of this system will be described. The current applications of this classical system will be discussed. Resins prepared from structurally modified phenols will be examined and labeled as modified-classical phenol-formaldehyde systems. The effect of these modifications on the mechanical, thermal, and other properties will be examined. Finally, the considerable work on polymers that can be classified as nonclassicaf phenolic resins will be presented and the area of nanocomposites utilizing phenolic resins will be examined. 

Including 4-bromophenol in the phenol-formaldehyde resol system impacts the cross-link density of the cured product. In a systematic study of this copolymer, a comparison was made among the polymers obtained using phenol only, a 9 1 mole ratio of phenol to 4-bromophenol and a 1 1 mole ratio of phenol to 4-bromophenol. Comparisons included measurement of interlaminar shear strength and cone calorimetry tests of composites prepared using these phenolic resins and S2-glass fiber plain weave. 

The development of ACF and AC cloths is closely related to that of carbon fibers (CFs). This makes that the raw materials used for the preparation of ACFs be, chronologically, the same as for CFs. Thus, in 1966, viscose and acetate cloths were, like for CFs, the first materials used to obtain ACFs [4, 5]. The low yield of the ACFs, and CFs, obtained from the above precursors, oriented the research towards the seek of other raw materials for the preparation of cheaper CFs and ACFs with a higher yield. In this way, ACFs were prepared from 1970 using lignin (with the brand of Kayacarbon ALF), polyvinylchloride [6] (i.e., Saran polymer, already used to obtain ACs) and phenolic precursors [7]. The high yield and the good mechanical properties of the ACFs obtained make these precursors very useful for this application. In fact. Economy and Lin [8] developed ACFs from a phenol formaldehyde precursor, which are commercialized since 1976 under the name of Novolak. In 1980, Kuray Chemical Co. Ltd commercialized ACFs from phenolic resin under the name of Kynol. ... 

Experimental attempts to synthesize any of the polymers described above have not been successful except a preliminary preparation of poly-perylene (Murakami and Yoshimura, 1984). Alternative efforts are currently being made to obtain polyacenic material through pyrolysis of various organic polymers such as phenol-formaldehyde resin (Yamabe et al., 1983 Tanaka et al., 1984b), polyacrylonitrile (Teoh et al., 1982, 1983), and poly(p-phenylene-1,3,4-oxadiazole) (Murakami et al., 1983). The group of these pyrolytic polymers behaves rather like amorphous semiconductors and is considered to be composed of fragments of polyacene to graphite, that is, a sort of coke, coal, and so on. 

The potential applications for conducting polymers are enormous and this has stimulated a large amount of research into this area. Not surprisingly, solid-state NMR spectroscopy has been applied to study these amorphous, insoluble and in many cases crosslinked materials [24]. Looking at the CP/MAS spectra of a series conducing polyacenic polymers, some of which were doped with iodine, it was possible to see the effect of the halogen upon conductivity. These resins were prepared by a conventional procedure for the preparation a Novolak-type phenol-formaldehyde resin. After synthesis, the phenol-formaldehyde resin were dissolved and solutions were cast as a film and heat treated to between 590-670°C in a N2 atmosphere to form the polyacenic film. The electrical conductivity of the films was shown to increase... 

A simple way to produce polymers with specific nitrogen functions in controlled concentration is to prepare phenol-formaldehyde resins in which part of the phenol is substituted by aniline (for amine-type nitrogen) or... 

Novolacs are linear polymers. Metacresol, a very reactive derivative of phenol, is typically used to prepare novolac resins. The presence of a methyl group at the meta (3 or 5) position of the henzene ring of phenol enhances the reactivity of the compound toward polymerization with formaldehyde. Novolac resins made with metacresol are also more moisture resistant than those with phenol. After preparation, novolac s ability to resist further polymerization is attributed to the fact that the chains terminate with phenol groupings, having been prepared with an excess of phenol. ... 

---