Starch with phenol-formaldehyde resins

Poly(vinyl alcohol) is utilized as a component of starch-based adhesives.11121114 Other patents report the use of partially oxidized starch,1115 dextrins,1116 dextrins and urea,1117 borax,1118 boric acid,1119 and vinyl methyl ether-maleic acid copolymers.1120 Other patents indicate the use of poly (vinyl alcohol) with partially hydrolyzed poly(vinyl acetate),1121 nonhy-drolyzed poly(vinyl acetate),1122 and poly(vinyl chloride).1123 A few patents have reported such poly acrylic additives as poly (acrylic acid)1124 and its salts,1125 poly(acrylamide),1126 1127 A-methylacrylamide or poly(A-acryl-amide),1128 and polyethyleneimine.1129 Polystyrene has also been used,1130 as well as more complex copolymers such as a maleic acid monobutyl ester-methyl vinyl ether copolymer, together with dextrin and polyacrylamide),1131 carboxylated ethyl acrylate-styrene zinc salt copolymer,1132 ethylene-methyl acrylate-vinyl acetate copolymer,1133 vinyl acetate-vinyl pyr-rolidone copolymer,1134 and ethylene-vinyl acetate copolymer.1135 Some adhesives are compounded with SBR latex1136 1138 and phenol-formaldehyde resins.1139... 

It was reported that the reaction of starch with phenol in the presence of a Lewis acid such as AICI3 resulted in resins of controlled melt viscosity.252 Probably, the product results from the hydrolysis of starch to glucose with conbversion of the latter into 5-(hydroxymethyl)-2-furaldehyde, which subsequently condensed with phenol.253 The reaction of starch with phenol without any catalyst required temperatures between 200 and 260 °C, and the resultant resinous product was then hardened by condensation with formaldehyde.254 Mastication of either glycerol or phenol with starch and water was said not to involve alcoholysis, but instead results in the formation of polymeric products.255 Reactions with gossypol256,257 and propylene glycol258 that were performed in the presence of a basic catalyst were in fact polymerization reactions and not alcoholyses. 

Materials from starch crosslinked with melamine-formaldehyde, methylated melamine-formaldehyde, and other amine-aldehyde resins were patented as binders for filter paper,1336 milk filter sheet materials,1338 and aqueous papercoating compositions containing clay, titanium(IV) oxide, butadiene-styrene latex, and calcium octadecanoate.1396,1397 Foams for filters were developed.1398 A heatsetting adhesive was one of the first applications reported for starch crosslinked by urea-formaldehyde and phenol-formaldehyde resins.1331,1340-1342,1347,1372,1399... 

The author has found the carbohydrate binders (e g. starch, dextrin) superior to phenol formaldehyde resins, maleic and phthalate type resins, polyester, glyptal resins, shellac, vegetable rosins, urea formaldehyde resin and melamine resin in all experiments to date. Dextrins and starches combine good binding properties and low cost with simple handling requirements. 

UF, urea-formaldehyde resin MUF, melamine fortified UF resin MF/MUF, melamine and melamine-urea resins (MF resins are only used mixed/coreacted with UF resins MUPF, melamine-urea-phenol-formaldehyde resin PF/PUF, phenol and phenol-urea-formaldehyde resin (P)RF, resoreinol-(phenol-)formaldehyde resin PMDI, polymeric methylenediisocyanate PVAc, polyvinylacetate adhesive old nat.adhesives, old (historic) natural adhesives (e.g., starch, glutin, casein adhesives) nat.adhesives, natural adhesives (e.g., tannins, lignins, carbohydrates) inorg.adhesives, inorganic adhesives (e.g., cement, gypsum) activation activation constituents of wood to function as adhesives (i.e., lignin). 

Glucoamylase immobilized with a glutaraldehyde-mediator on either phenol-formaldehyde resin or on silanized silica has been applied successfully to the saccharification of liquefied barley starch to obtain glucose syrups of up to DE 96. D-GIucose isomerase entrapped in cellulose beads and then glutaralde-... 

Polymers. AH nitro alcohols are sources of formaldehyde for cross-linking in polymers of urea, melamine, phenols, resorcinol, etc (see Amino RESINS AND PLASTICS). Nitrodiols and 2-hydroxymethyl-2-nitro-l,3-propanediol can be used as polyols to form polyester or polyurethane products (see Polyesters Urethane polymers). 2-Methyl-2-nitro-l-propanol is used in tires to promote the adhesion of mbber to tire cord (qv). Nitro alcohols are used as hardening agents in photographic processes, and 2-hydroxymethyl-2-nitro-l,3-propanediol is a cross-linking agent for starch adhesives, polyamides, urea resins, or wool, and in tanning operations (17—25). Wrinkle-resistant fabric with reduced free formaldehyde content is obtained by treatment with... 

By far the preponderance of the 3400 kt of current worldwide phenolic resin production is in the form of phenol-formaldehyde (PF) reaction products. Phenol and formaldehyde are currently two of the most available monomers on earth. About 6000 kt of phenol and 10,000 kt of formaldehyde (100% basis) were produced in 1998 [55,56]. The organic raw materials for synthesis of phenol and formaldehyde are cumene (derived from benzene and propylene) and methanol, respectively. These materials are, in turn, obtained from petroleum and natural gas at relatively low cost ([57], pp. 10-26 [58], pp. 1-30). Cost is one of the most important advantages of phenolics in most applications. It is critical to the acceptance of phenolics for wood panel manufacture. With the exception of urea-formaldehyde resins, PF resins are the lowest cost thermosetting resins available. In addition to its synthesis from low cost monomers, phenolic resin costs are often further reduced by extension with fillers such as clays, chalk, rags, wood flours, nutshell flours, grain flours, starches, lignins, tannins, and various other low eost materials. Often these fillers and extenders improve the performance of the phenolic for a particular use while reducing cost. 

The presence of numerous hydroxyl groups able to react with formaldehyde makes starch-derived products suitable chemicals for formaldehyde-based resins. Research on this subject started many years ago and showed that in a number of applications it is possible to partially replace or extend urea formaldehyde, phenol formaldehyde and melamine formaldehyde resins without significantly affecting the finished product s performance. In many applications, adhesive systems based on formaldehyde resins incorporate a polysaccharide component. More than 4.5 Mio mto of formaldehyde-based resins have been produced in Western Europe alone. The use of carbohydrates allows lower consumption of oil-based resins and, consequently, reduced release of formaldehyde in the environment. 

Water-based dispersions or emulsions such as polyvinyl acetate, acrylics, polyvinyl chloride and polyvinyl alcohol with plasticizers and tackifiers. In addition, this range can include urea formaldehyde and phenolic adhesives, resins, natural adhesives produced from starch, dextrin, casein, animal glues (see Polyvinyl alcohol in adhesives, Phenolic adhesives single-stage resoles. Phenolic adhesives two-stage novolacs. Animal glues and technical gelatins) and rubber latex (see Emulsion and dispersion adhesives). Solvent-free 100% solids such as polyurethane. Hot melt adhesives include Ethylene-vinyl acetate copolymers, polyolefins, polyamides, polyesters with tackifiers and waxes. More recent additions include cross-linkable systems. 

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