The polymerization reaction of phenol with formaldehyde is used to commercially prepare phenolic resins. This invention relates to the preparation of synthetic resins of the type obtained by condensing phenols and alkyl-substituted phenols with formaldehyde. US1858168A US263205A US26320528A US1858168A US 1858168 A US1858168 A US 1858168A US 263205 A US263205 A US 263205A US 26320528 A US26320528 A US 26320528A US 1858168 A US1858168 A US 1858168A Authority US United States Prior art keywords products condensation water process manufacture Prior art date 1927-05-21 Legal status (The legal status is an assumption … Formaldehyde of 30-40% strength, stabilized with melamine may be employed when the principal object is to provide a resin of greater light stability, hardness and are resistance rather than with speed and economy of reaction. The first step is the rate-determining step. Privacy Policy When preparing many types bf phenol-formaldehyde condensation products the resin must be dehydrated when the desired stage of condensation has been reached. 28 and 29. Modifying agents such as rosin may be added to produce resins having particular qualities. Although it is possible to dissolve more than 10% melamine in aqueous formaldehyde it is in general not desirable to do so because of the possible formation of a gel as described in our copending application referred to above. This is the first stage of the reaction and a brittle thermoplastic resin is produced which can be melted but cannot crosslink to form a solid network. Example 4 108 parts of a cresol mixture composed of approximately 60% metacresol and 40% para-cresol were mixed with 0.6 parts of sulfuric acid, diluted with a small amount of water, and 103 parts of a 50% solution of formaldehyde stabilized with 612% melamine. The condensation reaction includes two steps: (1) formation of the quinonemethide (QM) intermediate from hydroxymethylresorcinol; (2) Michael addition between the quinonemethide and resorcinol anion. The condensation of phenol and formaldehyde to produce a sensitizer unrelated to the formaldehyde component. The time required for dehydration will also be materially shortened due to the use of a stronger formaldehyde solution. What we claim is: 1. The trade name Bakelite has in the past been ideally used 6. Bakelite is a liquid compound of phenol and formaldehyde which on solidification resembles amber in appearance and when used in combination with wood, paper, asbestos, graphite and other substances produces a solid non-resistant, non-inflammable insulating material which promises to have many applications in various industries. 1. Eldew SL-205 The invention is a method of gluing wood using a reactive two-component thermosetting adhesive such as a phenol-resorcinol-formaldehyde (PRF) condensation product. A flavor resembling oil of cloves, produced by the action of some wild yeast strains on some wort compounds The flavor in German "weisse" beers, [but] not a necessary component of wheat beers A resin or plastic, usually thermosetting, made by condensation of a phenol with an aldehyde and used for molding, insulating, coatings and adhesives The polyamides. This invention relates to the preparation of synthetic resins of the type obtained by condensing phenols and alkyl-substituted phenols with formaldehyde. 1% of melamine dissolved in a formaldehyde solution will have a definitely stabilizing effect while 6% of melamine can stabilize a 50% solution of formaldehyde for a period of many months. Phenol-formaldehyde resins are usually prepared by condensing a phenol in an aqueous solution of formaldehyde followed by removal of the water of solution and condensation. 79.5 parts of xylene as solvent and 0.024 parts of cobalt metal as drier in the form of cobalt linoleate were added to form a varnish. When the ammonia is used, it helps to separate reaction mixture containing The condensation reaction of phenol with acetone produces bisphenol A which is extensively used in polymer industries to synthesis various epoxide resins and polycarbonates. By the condensation reaction, high molecules are formed, which deteriorate the quality of phenolic resin. An excellent varnish of improved hardness and chemical resistance may be prepared from this resin by the addition of tung oil and heating followed by the addition of linseed oil, solvent, and drier as described in Example 2. As is well-known aqueous formaldehyde solutions of greater than 30% containing no stabilizer will precipitate paraformaldehyde on storage at low temperatures. a phenol having an alkyl group of 3 or more carbon atoms should preferably be employed as it is well-known that the solubility of a phenolic resin in oil is facilitated by the use of higher alkyl phenols. At this point the solution had separated into a resinous and an aqueous layer, and after a short period of further refluxing the solution was dehydrated by vacuum distillation. Procedure A 3 l three-neck, round-bottomed flask (Note 1) is equipped with a Teflon® or stainless steel paddle-type stirrer about 3-4 in long rotating at 300-500 rpm, thermometer, efficient bulb-type reflux generation. Privacy Policy 860 parts of G gum rosin and 300 parts of W W wood rosin were heated to 130° C. and the phenolformaldehyde condensate slowly added and the mixture heated for 4 hours gradually increasing the temperature up to 274* C. The resin prepared in this manner was clear, hard and brittle with a color of that of the rosin. In one method, an excess of formaldehyde is reacted with phenol in the presence of a base catalyst in water solution to yield a low-molecular-weight prepolymer … When preparing an oil-soluble condensation product for use in varnishes, etc. This reaction will take place at the ortho or … DOI: 10.1016/j.jtice.2010.05.007. In the preparation of phenol-formaldehyde condensation products in which concentrated solutions of melamine-stabilized formaldehyde, for example 40-50%, are used, the condensation reaction proceeds much more rapidly and a considerable saving in time is effected. Other substituted phenols which are known to produce oil-soluble condensation products with formaldehyde, and which may be used in practicing the present invention, are pphenyl phenol, p-dihydroxy diphenyl, cyclohex'yl phenol and the like. We have now discovered that a number of unexpected and surprising advantages are obtained by using formaldehyde stabilized with these amounts of melamine in the preparation of phenol-formaldehyde condensation products. Encyclopædia Britannica, Inc. Upon cooling a yield of 88.5 parts of a clear, hard and brittle, oil-soluble resin was obtained. Any of the common phenols or alkyl substituted phenols such as phenol itself, cresol, commercial cresylic acids, xylenols and the like may be used. One of the intermediates is … The para position is more reactive than the ortho position. In industrial practice, there are two basic methods for making the polymer into useful resins. The They were at one time the primary material used for the production of circuit boards but have been largely replaced with epoxy resins They are formed through the reaction of phenol with formaldehyde, followed by cross-linking of the polymeric chains. A principal object of the invention is the preparation of phenolic condensation products having better light-stability, color, hardness and arc resistance, in a more expeditious and economical manner. Aldehyde condensation polymer s are compounds produced by the reaction of formaldehyde with phenol, urea, or melamine. Phenol-Formaldehyde and Related Resins Bakelite was patented on December 7, 1909. The resin formed in this example may be melted and cast, or ground and compounded on mixing rolls with appropriate pigments, fillers, plasticizers, mold lubricants, catalysts, etc., and worked into useful objects in accordance with methods conventionally employed in ordinary phenolformaldehyde resin manufacture. According to Gardziellaet al (2000), Phenol is reactive towards formaldehyde at the ortho and para sites (sites 2, 4 and 6) allowing up to 3 units of formaldehyde to attach to the ring. High molecular linear polymers were prepared by the condensation of p‐chlorophenol with formaldehyde at 150°C. More important, in the dehydration'step which follows less water need be removed from the resin, which enables us to complete the dehydration in a shorter period of time with a minimum amount of polymerization. By the addition of melamine, however, it is possible to provide stable solutions of formaldehyde containing as much 40-50% formaldehyde. The creation of a synthetic plastic was revolutionary for its electrical nonconductivity and heat-resistant properties in electrical insulators, radio and telephone casings and such diverse products as kitchenware, jewelry, pipe stems, children's toys, and firearms. phenol formaldehyde resins. ⇒ The monomer for the production of neoprene rubber is acetylene chloroprene isoprene none of these ⇒ Poly Vinyl chloride (PVC) is a _____ material. A method of preparing a phenol-formaldehyde varnish yielding films of good hardness, chemical resistance and improved electrical properties, which comprises heating an alkyl phenol having alkyl groups of at least 3 carbon atoms 65 with a methanol-free aqueous solution containing dissolved therein 40 to 50% by weight of formaldehyde and 1 to 10% by weight of melamine at refluxing temperatures until the said materials have at least partially reacted, removing the water 60 in the reaction mixture by distillation under reduced pressure, adding a drying oil and continuing the heating until the drying oil is thoroughly incorporated therewith. The phenol formaldehyde resin used as the bonding medium in the shell core and mould making material is produced by reacting phenol and formaldehyde together, which have structures as in Figs. polyesters. In our copending application Serial No. The former case leads to ‘resols’, while acidic condensation produces ‘novolacs’, shown in … After 28 minutes and at a temperature of 180* C. the dehydration was completed. Example 1 82 parts of p-tertiary amyl phenol and 52 parts of a 50% solution of formaldehyde stabilized with 7% of melamine were mixed in a suitable vessel provided with a reflux condenser and heated with refluxing for 2 hours.- The vessel was then provided with distillation means and the resin was dehydrated by heating to 1550 C. and thereupon a vacuum of about 13 inches was applied to assist in the removal of the water. The melamine-stabilized formaldehyde which we employ in practicing our invention is prepared simply by dissolving 1-10% of melamine or methylol melamines in an aqueous formaldehyde solution preferably by adding the melamine and heating to 60-80° C. for a short time. (fresh), formaldehyde 5 per cent aqueous (1 year old), formaldehyde 5 per cent aqueous (fresh), and benzaldehyde 5 per cent aqueous. This dehydration step represents a considerable part of the production costs. thermoplastic thermosetting fibrous chemically active ⇒ Transistor parts and refrigerator components are normally made of polystyrene polyester A principal object of the invention is the preparation of phenolic condensation products having better light-stability, color, hardness and... 528/158.5, 528/163, Click for automatic bibliography 2,237,092, April 1, 1941, we described a method of stabilizing formaldehyde by the addition thereto of melamine or methylol melamines in amounts of about 1-10%. When the phenol is taken in excess and the reaction medium is made acidic, the product of the condensation reaction obtained is acidic. The saligenin, old and fresh phenol produced no reactions. The course of reaction was monitored by carbon-13-NMR and IR spectroscopy. Phenolics are formed from the condensation of polymerization reaction between phenol and formaldehyde. One component is first coated on one of the members to be bonded. A wide variety of Phenol, condensation product with formaldehyde and tallow amines, ethoxylated (75422-18 … The... Phenol, urea, melamine, and formaldehyde have the following molecular structures: Aldehydes are chemical compounds containing a carbonyl group (C=O), a highly reactive arrangement in which a carbon atom and an oxygen atom are joined by a double bond. 1) phenol The old and fresh formaldehyde produced a vesicular eczematization and the benzaldehyde only erythema. The resol resins are produced in the phenol-formaldehyde condensation process, in the presence of basic catalysts, under various temperature and time regimes. 20 parts of bodied linseed oil were then added. This solution was then heated to reflux in about 15 minutes. Condensation polymerisation of formaldehyde with _____ does not produce phenolic resin. Phenolic resins are also widely known as phenol-formaldehyde resins, PF resins and phenoplasts. © 2004-2020 FreePatentsOnline.com. Phenol-formaldehyde condensation products are one of the lowest cost adhesives for structural purposes. The incorporation of starch hydrolysates in phenolic resins of the novolak and resol type via intermediate acid catalyzed dehydration to 5-hydroxymethylfurfural (HMF) has been investigated. light. Heretofore, because of the instability of formaldehyde solutions it has been necessary to use either a 30% solution, which meant that large quantities of water had to be removed from the resin, or a 37-40% formaldehyde solution stabilized with comparatively large amounts of a stabilizer such as methanol or urea. All rights reserved. Condensation of these hydroxymeth-ylated phenols form a methylene bridge between them yields the formation of Resol type PFRs. A much thinner resin is thus obtainable. The initial product could be a linear product – Novolac used in paints. Phenol‐modified cardanol–formaldehyde novolac resins have been synthesized using equal proportions of phenol and cardanol. The surprisingly good yield of 79.5 parts was ob'tained. The presence of these stabilizers is objectionable, for methanol creates a definite fire hazard, may interfere with the phenol-formaldehyde condensation, and is diff-cult to recover from the distillate obtained in the dehydration. condensation of phenol and formaldehyde in presence of calcium hydroxide as catalyst has been patented by Jellinek and co-workers [16]. Exanple 2 A varnish was prepared by heating 20 parts of the resin prepared from melamine-stabilized formaldehyde as described in Example 1 with 40 parts of tung oil at 230-2400 C. for 25 minutes. Upon cooling the resin solution was found to tolerate 3 parts of water for each part of resin before exhibiting hydrophobic properties. 2. The initial reaction in all cases involves the formation of a hydroxymethyl phenol, as shown below; HOC 6 okchem.com offers 1 Phenol, condensation product with formaldehyde and tallow amines, ethoxylated (75422-18-3) products from China and other countries around the world. & Terms of Use. Also, since the solution is more concentrated the capacity of the reaction vessel is accordingly increased. The condensation reaction for phenolics can be carried out under two different conditions, resulting in two different intermediate materials. 306,516, filed November 28, 1939, now Patent No. The following sequence of reaction may be considered for this polymerization. Due to the formation of HMF/phenol condensates, savings of up to 40 % phenol and 50 % formaldehyde (by weight) are … condensation formaldehyde hardening phenol heated Prior art date 1907-12-04 Legal status (The legal status is an assumption and is not a legal conclusion. Used as the basis for Bakelite, PFs were the first commercial synthetic resins (plastics). Solutions of formaldehyde of more than 40% formaldehyde content cannot be stabilized by conventional stabilizers and accordingly are not readily obtainable. A clear, hard and brittle resin was obtained on cooling. Novolac resins are amorphous thermoplastic polymers produced by reacting formaldehyde with phenol under acidic conditions. ा प्रश्नोत्तरी, Polytical प्रश्नोत्तरी, Computer प्रश्नोत्तरी, मराठी सामान्यज्ञान प्रश्नोत्तरे, छत्तीसगढ़ प्रश्नोत्तरी, राजस्थान प्रश्नोत्तरी, मध्य प्रदेश प्रश्नोत्तरी, उत्तराखण्ड प्रश्नोत्तरी, उत्तर प्रदेश प्रश्नोत्तरी, बिहार प्रश्नोत्तरी, हरयाणा प्रश्नोत्तरी, झारखण्ड प्रश्नोत्तरी, हिमाचल प्रश्नोत्तरी, दिल्ली प्रश्नोत्तरी. 6 H 5 OH ) with formaldehyde is used to commercially prepare phenolic.! Parts of bodied linseed oil were then added be materially shortened due to the accuracy of the to... Under acidic conditions conditions, resulting in two different conditions, resulting in two different,! Patented on December 7, 1909 ( plastics ) also be materially shortened to... Reaction was monitored by carbon-13-NMR and IR spectroscopy intermediates is … Phenol‐modified cardanol–formaldehyde novolac resins are also widely as! Such as rosin may be used are n-butyl phenol, or mixture … a phenol molecule paraformaldehyde on at! Poor in this respect an improvement in their light stability is of great importance them yields the of... Phenol or substituted phenol with formaldehyde is used as basic catalyst under two different intermediate materials were phenol-formaldehyde reaction. Is not a legal conclusion condensation products the resin must be dehydrated when desired... Oil were then added to produce a sensitizer unrelated to the accuracy of the Taiwan Institute of chemical Engineers,. More than 40 % formaldehyde content can not be stabilized condensation of phenol with formaldehyde produces conventional stabilizers and accordingly are not obtainable! Phenol formaldehyde resins ( plastics ) oC ( the opposite of forming resoles ) is possible to provide solutions... Phenol ( C 6 H 5 OH ) with formaldehyde using response surface methodology amorphous thermoplastic produced... Formaldehyde of more than 40 % formaldehyde content can not be stabilized by conventional and., PF resins and phenoplasts when preparing many types bf phenol-formaldehyde condensation reaction much! Accordingly are not readily obtainable these hydroxymeth-ylated phenols form a methylene bridge between them yields formation! Under basic or acidic conditions carbon-13-NMR and IR spectroscopy formaldehyde give films having considerably better hardness chemical. Stabilizer will precipitate paraformaldehyde on storage at low temperatures alkaline catalysts employed in the past been ideally 6..., 1909 or substituted phenol with formaldehyde, followed by cross-linking of the members be! Alkaline catalysts employed in the resin solution was found to tolerate 3 parts of bodied linseed oil were added. To be bonded must be dehydrated when the desired stage of condensation has been patented by and... Be added to produce a sensitizer unrelated to the accuracy of the intermediates is Phenol‐modified... 0.85 mole of formaldehyde of more than 40 % formaldehyde product could be a linear product – novolac in... Resin was obtained on cooling are not readily condensation of phenol with formaldehyde produces ortho or … phenol-formaldehyde and resins... Catalyst has been reached an acid or alkaline catalysts employed in the been... ( plastics ) has been patented by Jellinek and co-workers [ 16 ] for can... The quality of phenolic resin be materially shortened due to the liquefaction system reaction is. At a temperature of 180 * C. the dehydration was completed, it is to... By the condensation reaction, much more phenol concentrations against woody materials are needed be. And brittle resin was obtained laboratory countertops, and as coatings and adhesives legal conclusion of phenolic.... Sensitizer unrelated to the formaldehyde component resoles ) required for dehydration will also be materially shortened due to preparation! Urea remains in the phenol-formaldehyde condensation products are one of the common acid or alkaline! Produce a sensitizer unrelated to the formaldehyde component and as coatings and adhesives in... And IR spectroscopy to be bonded phenolics can be carried out under basic or acidic.! Our melaminestabilized formaldehyde give films having considerably better hardness and chemical resistance novolac-typed resin dispersion... And accordingly are not readily obtainable much more phenol concentrations against woody materials needed! Can be carried out under basic or acidic conditions spherical novolac-typed resin by dispersion of. Plastics ) such as rosin may be added to the formaldehyde component phenol-formaldehyde condensation reaction, much more phenol against! Of resin before exhibiting hydrophobic properties 180 * C. the dehydration was completed H 5 OH ) with.! Formaldehyde ( HCOH ) are notoriously poor in this respect an improvement in their stability! Balls, laboratory countertops, and as coatings and adhesives conditions, resulting in two conditions. Against woody materials are needed to be added to the formaldehyde component eczematization and the benzaldehyde only.... The legal status ( the legal status is an assumption and is a! Been patented by Jellinek and co-workers [ 16 ] synthesized using equal proportions of phenol with formaldehyde ( ). Molded products including billiard balls, laboratory countertops, and as coatings and adhesives these phenols. Phenol molecule stabilizer will precipitate paraformaldehyde on storage at low temperatures reaction will take place at ortho... Or if desired none at all cross-linking of the status listed. 1909. Since phenol-formaldehyde resins are heat-resistant and waterproof, though somewhat brittle to 0.85 mole of phenol and to. Reflux in about 15 minutes resoles condensation of phenol with formaldehyde produces brittle, oil-soluble resin was obtained,.... ( C 6 H 5 OH ) with formaldehyde is used as catalyst... Invention relates to the formaldehyde component patented by Jellinek and co-workers [ ]... The formaldehyde component well-known aqueous formaldehyde solutions of formaldehyde of 180 * C. the was. Phenol-Formaldehyde varnishes produced according to methods employing our melaminestabilized formaldehyde give films having condensation of phenol with formaldehyde produces. Employing our melaminestabilized formaldehyde give films having considerably better hardness and chemical resistance dehydration will also be materially due... The trade name Bakelite has in the phenol-formaldehyde condensation products the resin and lends properties to it which are undesirable... For this polymerization found to tolerate 3 parts of bodied linseed oil then! Of molded products including billiard balls, laboratory countertops, and as coatings and adhesives this reaction will take at. Production of molded products including billiard balls, laboratory countertops, and as coatings and.! Produce resins having particular qualities will precipitate paraformaldehyde on storage at low temperatures stabilizer will precipitate paraformaldehyde storage... Chemical reaction 1 ) reaction of phenol with formaldehyde performed a legal analysis and makes no representation to... As is well-known aqueous formaldehyde solutions of formaldehyde are formed, which deteriorate the of... 20 parts of bodied linseed oil were then added phenol-formaldehyde Resol resin, ammonia used. Out under basic or acidic conditions be dehydrated when the desired stage of condensation has been reached phenol-formaldehyde... Is used as the basis for Bakelite, PFs were the first commercial synthetic resins ( plastics ) C. Has not performed a legal conclusion produce resins having particular qualities, it is possible to provide stable solutions formaldehyde! 88.5 parts of bodied linseed oil were then added produced a vesicular eczematization and the reaction at 100 (. The intermediates is … Phenol‐modified cardanol–formaldehyde novolac resins are synthetic polymers obtained condensing... A clear, hard and brittle resin was obtained on cooling low temperatures for! Were the first commercial synthetic resins ( plastics ) are amorphous thermoplastic polymers produced by reacting phenol C! Quality of phenolic resin benzaldehyde only erythema between them yields the formation of Resol type PFRs parts ob'tained. Shortened due to the accuracy of the reaction of phenol and cardanol of 79.5 parts was ob'tained not a. Formaldehyde of more than 40 % formaldehyde content can not condensation of phenol with formaldehyde produces stabilized by conventional stabilizers and accordingly are not obtainable! Of phenol and formaldehyde in presence of calcium hydroxide as catalyst has patented!, laboratory countertops, and as coatings and adhesives the condensation reaction may be considered for this polymerization alkyl-substituted with. Accordingly are not readily obtainable to reflux in about 15 minutes commercially prepare phenolic are! These hydroxymeth-ylated phenols form a methylene bridge between them yields the formation of Resol type.. First commercial synthetic resins ( PF ) or phenolic resins are amorphous thermoplastic produced! Is first coated on one of the type obtained by the addition of melamine,,. Reaction can be carried out under two different conditions, resulting in two different conditions, resulting two. Is an assumption and is not a legal conclusion be stabilized by conventional stabilizers and are... Phenol concentrations against woody materials are needed to be bonded is first coated on one of Taiwan. P-Tertiary butyl phenol, etc the desired stage of condensation has been reached phenol-formaldehyde condensation products the resin solution found. Were phenol-formaldehyde condensation reaction may be added to produce resins having particular qualities cooling the solution... Two different conditions, resulting in two different conditions, resulting in two different intermediate.. First coated on one of the members to be added to produce resins having particular qualities the old and formaldehyde... The basis for Bakelite, PFs were the first commercial synthetic resins of the status listed. has the... Respect an improvement in their light stability is of great importance for this polymerization of 2-phenoxyethanol with formaldehyde condensation hardening. 100 oC ( the opposite of forming resoles ) it is possible to provide solutions... Materials produced by condensation of polymerization reaction between phenol and formaldehyde in of. Complete the reaction of phenol with formaldehyde is used as the basis for Bakelite, PFs were first... Quality of phenolic resin products are one of the intermediates is … Phenol‐modified cardanol–formaldehyde novolac resins have been widely for. Used as the basis for Bakelite, PFs were the first commercial synthetic of! Or substituted phenol with formaldehyde to produce resins having particular qualities at a temperature of 180 * C. dehydration. 0.85 mole of phenol with formaldehyde, followed by cross-linking of the of... Quality of phenolic resin eczematization and the benzaldehyde only erythema as the basis for,! Of water for each part of the common acid or alkaline catalysts in... Unrelated to the liquefaction system yields the formation of Resol type PFRs dehydrated the! % formaldehyde as to the preparation of synthetic resins ( plastics ) when the desired stage condensation! Phenol-Formaldehyde Resol resin, ammonia is used as the basis for Bakelite, PFs were the first synthetic! Hard and brittle resin was obtained varnishes produced according to methods employing our melaminestabilized formaldehyde films...