Resin acids emulsion

Crude tall oil is a mixture of fatty acids, resin acids, and neutrals (i.e., no carboxylic acid functionality). The background section relates that neutrals interfere with the separation of the fatty acids from the resin acids and in industrial practice the neutrals are removed by molecul distillation. However, it is difficult to separate the neutrals from the other components because of vapor pressure similarity considerations. Tall oil soap, the precursor to crude tall oil, is a pasty emulsion of the neutrals and the sodium salts of the fatty and resin acids. The patent states that it is possible to extract neutrals from the soap with a liquid hydrocarbon solvent, but the prior art discussion relates that subsequent liquid hydrocarbon solvent recovery steps are relatively difficult. The neutrals can be separated from the soaps by a hydrocarbon solvent, incidentally, because the neutrals are lipophiles whereas the soaps are ionic and do not dissolve in the hydrocarbon. Similarly the neutrals will dissolve in a supercritical fluid like ethylene, or propane, or the chlorofluorocarbons, and the use of these gases in the supercritical state is the invention. Like the case of liquid hydrocarbon solvents, the ionic soap compounds will not dissolve in the supercritical gases. CO2 is specifically not listed among the gases, and we shall discuss the case of CO2 extraction of the emulsion later which is the subject of the next patent. 

The strongest films are formed under the most acidic conditions. Finally, the films least able to relax under reduced surface stress conditions were observed to form the most stable emulsions. They also found that components other than asphaltenes, such as alkanes (paraffin waxes), resins, and aged interfacially active components of relatively high H/C ratio (1 5), can also contribute to the stabilization of water-in-crude oil emulsions. They concluded that the state of solvation of asphaltenes in the oil phase plays an important role in their ability to stabilize emulsions, which may explain the indirect action of resins on emulsion stability. The temperature is also an important factor when it comes to the stability of crude oil emulsions, especially true when the wax content is relatively high. The most important factor influencing the water-in-crude oil emulsion stability at low temperature is the interaction at the water-oil interface between wax crystals and the heavy fractions of the crude. 

Rosin exploitation, a part of the so-called Naval Stores Industry, is at least as old as the construction of wooden naval vessels. In recent years, rosin components have attracted a renewed attention, notably as sources of monomers for polymers synthesis. The purpose of the present chapter is to provide a general overview of the major sources and composition of rosin. It deals therefore with essential features such as the structure and chemical reactivity of its most important components, viz. the resin acids, and the synthesis of a variety of their derivatives. This chemical approach is then followed hy a detailed discussion of the relevant applications, the resin acids and their derivatives, namely in polymer synthesis and processing, paper sizing, emulsion polymerization, adhesive tack and printing inks, among others. 

Rosin, Resin acids. Chemical modification. Paper sizing. Emulsion polymerization. Adhesive tack. Polymer chemistry and processing. Printing inks... 

PS/PU hybrid latex particles were synthesised using water soluble or dispersible PU resins as emulsifiers. Two kinds of PU resins were prepared from isophorone diisocyanate, poly(l,2-propylene glycol)s and 2,2-bis(hydroxymethyl)-propionic acid. Emulsion polymerisation of styrene with the PU resins showed similar kinetic dependence on stabiliser and initiator concentration as with conventional... 

Rectification tar oils Fatty acid and resin acid Oleic acid 28 3 % Linoleic acid 38-65 %, Linolenic acid 0.5-2.0 % Stearic acid 4—10 % Palm acid 4-10 % Class A, B organic acid 92-95 %, Resin acid <40 % Acid value 150-158 Soap value 160-170 Fractionate crade tar oils at 200-235 °C Making up 1-10 % emulsion or 1-15 % saponified fluid Mixing with anionic collector... 

Tar oil fatty acid The proportion of oleic acid and linoleic acid 1 1 and some unsaponifiable matter Class A, B resin acid<2% Class B resin acid <3% Class F resin aeid 18-25 % Unsaponifiable matter content Class A <3 % Class B <5 % Class B, F 4 % Acid value 180 1-10 % emulsion, 1-15 % caustic soda, saponified fluid... 

The discovery in 1807 that water resistance in paper could be achieved by precipitating partially saponified rosin with alum on pulp led to a market that has been the major use of rosin for many years. In addition to the simple aqueous dispersion of sodium resinate, called paste size, rosin sizes in emulsion and dry form are also used. The composition of the rosin, the amount of neutrals and oxidized components as well as the resin acid composion, affects the efficacy and physical properties of a size. The efficiency of rosin sizes is improved by fortifica-... 

The alternative route of preparing water reducible resins using emulsion polymerisation of an acid functional acrylic resin has already been considered under emulsion example 7 - preparation of a water soluble acrylic copolymer. 

Melamine formaldehyde can be crosslinked at elevated temperatures with both hydroxyl and carboxyl functional groups. (See thermosetting acrylics chapter for reaction mechanisms.) The temperature required is at least 120°C, at which point the hydroxyl group will react, but the carboxyl group needs a slightly higher heat input, approximately 150°C. Systems are unlikely to require an acid catalyst because of the catalytic effects of the polymerisation catalysts and surfactants in the acrylic latices. If required, p-toluene sulphonic acid is the most suitable (typically at levels of 0.2 - 0.4%). Alternatively, the melamine resin could be incorporated in an unneutralised, acidic emulsion, which reduces the cure temperature, but will sacrifice stability. 

Figure 3.4 Distribution of resin acids and fatty acids between lipophilic phase and water phase at 50 °C and tow NaCt concentration in wood pitch emulsion.

Solution vehicles consist of water soluble polymers not manufactured by emulsion polymerization. The solution vehicle is an alkali soluble polymer in aqueous solution or a blend of polymers with combined properties into a single waterborne varnish. Soluble polymers are made by free radical polymerization in a processing solvent or as addition or condensation products with heat reaching temperatures up to 265 °C. Solution vehicles are mixtures of soluble resins unlike emulsion polymers. A solution vehicle is used to increase adhesion to film and improve ink printabihty or transfer to meet specific performance requirements. The solution vehicle provides pigment dispersion stabilization, transparency, low film forming temperature, gloss and re-solubility. An alkali soluble resin is a carboxylic acid functional polymer neutralized (solubilized) with ammonia, amine or sodium hydroxide. The add numbers are generally above 100. Ammonia or volatile amines are used in most aqueous inks except for news print inks. After evaporation of the amine, the resin becomes insoluble and resistant to water spray or other water contact. The ink is re-solubilized with alkaline water for the clean-up cycle. For news print ink, the polymers are solubiHzed with sodium hydroxide to maintain re-solubility (open time) of the ink on the press. News print ink pressman prefer unlimited open time and fewer clean-up cycles. Water resistance is not required since ink penetrates the news print paper fibers. 

Most of the acetic acid is produced in the United States, Germany, Great Britain, Japan, France, Canada, and Mexico. Total annual production in these countries is close to four million tons. Uses include the manufacture of vinyl acetate [108-05-4] and acetic anhydride [108-24-7]. Vinyl acetate is used to make latex emulsion resins for paints, adhesives, paper coatings, and textile finishing agents. Acetic anhydride is used in making cellulose acetate fibers, cigarette filter tow, and ceUulosic plastics. 

Acrylics. Acetone is converted via the intermediate acetone cyanohydrin to the monomer methyl methacrylate (MMA) [80-62-6]. The MMA is polymerized to poly(methyl methacrylate) (PMMA) to make the familiar clear acryUc sheet. PMMA is also used in mol ding and extmsion powders. Hydrolysis of acetone cyanohydrin gives methacrylic acid (MAA), a monomer which goes direcdy into acryUc latexes, carboxylated styrene—butadiene polymers, or ethylene—MAA ionomers. As part of the methacrylic stmcture, acetone is found in the following major end use products acryUc sheet mol ding resins, impact modifiers and processing aids, acryUc film, ABS and polyester resin modifiers, surface coatings, acryUc lacquers, emulsion polymers, petroleum chemicals, and various copolymers (see METHACRYLIC ACID AND DERIVATIVES METHACRYLIC POLYMERS). 

Inversion ofMon cjueous Polymers. Many polymers such as polyurethanes, polyesters, polypropylene, epoxy resins (qv), and siHcones that cannot be made via emulsion polymerization are converted into latices. Such polymers are dissolved in solvent and inverted via emulsification, foUowed by solvent stripping (80). SoHd polymers are milled with long-chain fatty acids and diluted in weak alkaH solutions until dispersion occurs (81). Such latices usually have lower polymer concentrations after the solvent has been removed. For commercial uses the latex soHds are increased by techniques such as creaming. 

Quarpel is an important combination of fluorochemical finish and resin-based extender developed by the U.S. Army Natick Laboratories for military use. This finish typicaUy contains 4—6 wt % commercial fluorochemical emulsion, 4—6 wt % resin-based repeUent emulsion, 0.1 wt % acetic acid, and 5 wt % isopropyl alcohol. If necessary, the formulation includes a catalyst to cross-link the resin-based component. Quarpel specifications demand exceUent initial water and oU repeUency and exceUent durabUity to washing and dry cleaning. 

The basic patent (US Patent 3256219) indicates that the system is viable with conventional resins although special grades have been developed that are said to be particularly suitable. One example in the patent recommends the use of a polyester prepared using a maleic acid, phthalic acid and propylene glycol ratio of 2 1 33 and with an acid value of 40. To 500g of such a resin are added 10g of benzoyl peroxide and 167 g of styrene. Water 600 g is then stirred in at 5-10°C until a white creamy water-in-oil emulsion is obtained. A solution of 0.8 g of dimethyl-p-toluidine in lOOg of styrene is stirred into the emulsion and the resin is cast between plates and cured at 50°C. 

Dithiobenzoic acid metal complexes, 2, 646 colours, 2, 646 Dithiobiuret metal complexes, 2, 640 Dithiocarbamates chelating resins mineral processing, 6,826 Dithiocarbamic acid metal complexes, 2,585 amine exchange, 1,428 photographic emulsions, 6,98 nickel poisoning, 6,768 tellurium(Il) complexes photothermography, 6,121 Dithiocarbazic acid metal complexes, 2,803 Dithiocarbimic acid metal complexes, 2,588 Dithiocarbimic acid, cyano-metal complexes, 2,808 Dithiocarboxylic acids metal complexes, 2,646 Dithiodiacetic acid metal complexes, 2, 806 Dithiodiketones... 

The carboxylated polymers [476,499] include acrylic, methacrylic or maleic acid polymers (all obviously anionic in character) applied mainly from aqueous emulsion and particularly in combination with crease-resist or durable press resins. This type of chemistry has already been discussed in section 10.8.2. A particularly common example is the copolymer of acrylic acid with ethyl acrylate (10.247). In general the best balance of properties is obtained with 75-85% ethyl acrylate (y) and 25-15% acrylic acid (x), with an average chain length of about 1300 (x + y) units 65-85% ethyl acrylate with 35-15% methacrylic acid is also suitable. When the content of the acidic comonomer increases above about 30% the durability to washing tends to decrease, whilst longer chains tend to give a stiffer handle [499]. 

Emulsion paints are based on aqueous synthetic resin dispersions, which afford a lacquer-like paint film. The resin dispersions which are commonly used by the paint industry contain water as the carrier phase. A large number of such dispersions are available, based on different resins such as poly(vinyl acetate), which may be employed as a copolymer with vinyl chloride, maleic dibutyl ester, ethylene, acrylic acid esters, polyacrylic resin, and copolymers of the latter with various monomers, as well as styrene-butadiene or poly(vinyl propionate). These disper-... 

P.Y.108 is applied in various types of industrial finishes, especially in original automotive (O.E.M) and in automotive refinishes. It is also recommended for metallic finishes, although it is much less weatherfast in such systems. The pigment tends to seed, i.e., it forms specks upon storage. The mechanism behind this phenomenon remains to be elucidated. Besides, P.Y.108 also lends color to emulsion paints, in which it is durable enough to satisfy the requirements for exterior paints based on synthetic resin dispersions. It is also fast to acids, alkali, and plaster. 

In a small round-bottomed flask the ethereal mother liquor is concentrated to a volume of 10 c.c., 50 c.c. of low-boiling petrol ether are added, and the stoppered flask is shaken continuously until a clear solution is obtained. The petrol ether which is now poured out contains/uWy adds and cholesterol, whereas the bile acids formerly in solution in the ether have separated as a thick resinous mass. In order to separate the fatty acids and the cholesterol the petrol ether solution is carefully shaken with 50 to 60 c.c. of 2iV-potas-sium hydroxide solution. This solution is added in 10 c.c. portions, and each portion is at once removed so as to avoid emulsions. 

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