Poly emulsifier

Emulsion Adhesives. The most widely used emulsion-based adhesive is that based upon poly(vinyl acetate)—poly(vinyl alcohol) copolymers formed by free-radical polymerization in an emulsion system. Poly(vinyl alcohol) is typically formed by hydrolysis of the poly(vinyl acetate). The properties of the emulsion are derived from the polymer employed in the polymerization as weU as from the system used to emulsify the polymer in water. The emulsion is stabilized by a combination of a surfactant plus a coUoid protection system. The protective coUoids are similar to those used paint (qv) to stabilize latex. For poly(vinyl acetate), the protective coUoids are isolated from natural gums and ceUulosic resins (carboxymethylceUulose or hydroxyethjdceUulose). The hydroHzed polymer may also be used. The physical properties of the poly(vinyl acetate) polymer can be modified by changing the co-monomer used in the polymerization. Any material which is free-radically active and participates in an emulsion polymerization can be employed. Plasticizers (qv), tackifiers, viscosity modifiers, solvents (added to coalesce the emulsion particles), fillers, humectants, and other materials are often added to the adhesive to meet specifications for the intended appHcation. Because the presence of foam in the bond line could decrease performance of the adhesion joint, agents that control the amount of air entrapped in an adhesive bond must be added. Biocides are also necessary many of the materials that are used to stabilize poly(vinyl acetate) emulsions are natural products. Poly(vinyl acetate) adhesives known as "white glue" or "carpenter s glue" are available under a number of different trade names. AppHcations are found mosdy in the area of adhesion to paper and wood (see Vinyl polymers). 

The viscosity of the latex can also be dependent on pH. In the case of some latices, lowering the pH with a weak acid such as glycine is an effective method for raising the viscosity without destabilising the system. Latices made with poly(vinyl alcohol) as the primary emulsifier can be thickened by increasing the pH with a strong alkaU. 

Figure 5 illustrates the type of encapsulation process shown in Figure 4a when the core material is a water-immiscible Hquid. Reactant X, a multihmctional acid chloride, isocyanate, or combination of these reactants, is dissolved in the core material. The resulting mixture is emulsified in an aqueous phase that contains an emulsifier such as partially hydroly2ed poly(vinyl alcohol) or a lignosulfonate. Reactant Y, a multihmctional amine or combination of amines such as ethylenediamine, hexamethylenediamine, or triethylenetetramine, is added to the aqueous phase thereby initiating interfacial polymerisation and formation of a capsule shell. If reactant X is an acid chloride, base is added to the aqueous phase in order to act as an acid scavenger. 

Lignites and lignosulfonates can act as o/w emulsifiers, but generally are added for other purposes. Various anionic surfactants, including alkylarylsulfonates and alkylaryl sulfates and poly(ethylene oxide) derivatives of fatty acids, esters, and others, are used. Very Httle oil is added to water-base muds in use offshore for environmental reasons. A nonionic poly(ethylene oxide) derivative of nonylphenol [9016-45-9] is used in calcium-treated muds (126). 

Emulsions of fatty- and petroleum-based substances, both oils and waxes, of the o/w type are made by using blends of sorbitan fatty esters and their poly(oxyethylene) derivatives. Mixtures of poly(oxyethylene(20)) sorbitan monostearate (Polysorbate 60) and sorbitan monostearate are typical examples of blends used for lotions and creams. Both sorbitan fatty acid esters and their poly(oxyethylene) derivatives are particularly advantageous in cosmetic uses because of their very low skin irritant properties. Sorbitan fatty ester emulsifiers for w/o emulsions of mineral oil are used in hair preparations of both the lotion and cream type. Poly(oxyethylene(20)) sorbitan monolaurate is useflil in shampoo formulations (see Hairpreparations). Poly(oxyethylene) sorbitan surfactants are also used for solubilization of essential oils in the preparation of colognes and after-shave lotions. 

Eatty acid ethoxylates are used extensively in the textile industry as emulsifiers for processing oils, antistatic agents (qv), softeners, and fiber lubricants, and as detergents in scouring operations. They also find appHcation as emulsifiers in cosmetic preparations and pesticide formulations. Eatty acid ethoxylates are manufactured either by alkaH-catalyzed reaction of fatty acids with ethylene oxide or by acid-catalyzed esterification of fatty acids with preformed poly(ethylene glycol). Deodorization steps are commonly incorporated into the manufacturing process. 

Emulsion Polymerization. Poly(vinyl acetate)-based emulsion polymers are produced by the polymerization of an emulsified monomer through free-radicals generated by an initiator system. Descriptions of the technology may be found in several references (35—39). 

Poly(vinyl acetate) emulsions can be made with a surfactant alone or with a protective coUoid alone, but the usual practice is to use a combination of the two. Normally, up to 3 wt % stabilizers may be included in the recipe, but when water sensitivity or tack of the wet film is desired, as in some adhesives, more may be included. The most commonly used surfactants are the anionic sulfates and sulfonates, but cationic emulsifiers and nonionics are also suitable. Indeed, some emulsion compounding formulas require the use of cationic or nonionic surfactants for stable formulations. The most commonly used protective coUoids are poly(vinyl alcohol) and hydroxyethyl cellulose, but there are many others, natural and synthetic, which are usable if not preferable for a given appHcation. 

Issues to be considered in selecting the best stabilizing system are polymeric chain branching which increases with high temperature and the presence of some stabilizers, polydispersity of the particles produced, and grafting copolymerization, which may occur because of the reaction of vinyl acetate with emulsifiers such as poly(vinyl alcohol) (43,44). 

Chain transfer also occurs to the emulsifying agents, leading to their permanent iacorporation iato the product. Chain transfer to aldehydes, which may be formed as a result of the hydrolysis of the vinyl acetate monomer, tends to lower the molecular weight and slow the polymerisation rate because of the lower activity of the radical that is formed. Thus, the presence of acetaldehyde condensates as a poly(vinyl alcohol) impurity strongly retards polymerisation (91). Some of the initiators such as lauryl peroxide are also chain-transfer agents and lower the molecular weight of the product. 

Partially hydrolyzed grades are used in many cosmetic appHcations for their emulsifying, thickening, and film-forming properties. Poly(vinyl alcohol) is also used as a viscosity builder for aqueous solutions and dispersions. 

Salts of neodecanoic acid have been used in the preparation of supported catalysts, such as silver neodecanoate for the preparation of ethylene oxide catalysts (119), and the nickel soap in the preparation of a hydrogenation catalyst (120). Metal neodecanoates, such as magnesium, lead, calcium, and zinc, are used to improve the adherence of plasticized poly(vinyl butyral) sheet to safety glass in car windshields (121). Platinum complexes using neodecanoic acid have been studied for antitumor activity (122). Neodecanoic acid and its esters are used in cosmetics as emoUients, emulsifiers, and solubilizers (77,123,124). Zinc or copper salts of neoacids are used as preservatives for wood (125). 

Dichlorobenzene is consumed for 3,4-dich1oroani1ine, the base material for several herbicides, in the United States and Western Europe and is emulsified in Japan for garbage treatment. The greatest market worldwide for -dichlorobenzene is for deodorant blocks and moth control. A growing use for -dichlorobenzene is the manufacture of poly(phenylene sulfide) (PPS) resins. 

Certain block copolymers have also found appHcation as surfactants (88). Eor example, AB or ABA block copolymers in which one block is hydrophilic and one block is hydrophobic have proven useful for emulsifying aqueous and non-aqueous substances and for wetting the surface of materials. Examples of such surfactants are the poly(propylene oxide- /oi / -ethylene oxide) materials, known as Pluronics (BASC Wyandotte Co.). 

Accurate information oa the size of the defoamer market is impossible to obtaia. There are too many types of materials and suppHers iavolved. Particularly for the more common oils and surfactants, defoaming is a very small part of their total usage, and no pubHc information is available on what fraction of manufacturers sales is ia the area of foam coatrol. Evea for more expeasive materials such as the poly(alkyleae oxide) block copolymers, there is ao way of distinguishing betweea their use as defoamers and other significant surfactant uses such as de-emulsifiers. 

Fig. 11. In a system of water and hydrocarbon a nonionic emulsifier with a poly(ethylene glycol) chain as the polar part dissolves in the aqueous phase at low temperatures (a) and in the oil phase at high temperatures (c). At an intermediate temperature (b) three isotropic Hquid phases may be found.

Since poly(vinyl acetate) is usually used in an emulsion form, the emulsion polymerisation process is commonly used. In a typical system, approximately equal quantities of vinyl acetate and water are stirred together in the presence of a suitable colloid-emulsifier system, such as poly(vinyl alcohol) and sodium lauryl sulphate, and a water-soluble initiator such as potassium persulphate. 

Poly(vinyl acetate) is too soft and shows excessive cold flow for use in moulded plastics. This is no doubt associated with the fact that the glass transition temperature of 28°C is little above the usual ambient temperatures and in fact in many places at various times the glass temperature may be the lower. It has a density of 1.19 g/cm and a refractive index of 1.47. Commercial polymers are atactic and, since they do not crystallise, transparent (if free from emulsifier). They are successfully used in emulsion paints, as adhesives for textiles, paper and wood, as a sizing material and as a permanent starch . A number of grades are supplied by manufacturers which differ in molecular weight and in the nature of comonomers (e.g. vinyl maleate) which are commonly used (see Section 14.4.4)... 

Poly(vinyl alcohol) will function as a non-ionic surface active agent and is used in suspension polymerisation as a protective colloid. In many applications it serves as a binder and thickener is addition to an emulsifying agent. The polymer is also employed in adhesives, binders, paper sizing, paper coatings, textile sizing, ceramics, cosmetics and as a steel quenchant. 

In another study, uniform composite polymethyl-methacrylate/polystyrene (PMMA/PS) composite particles in the size range of 1-10 fim were prepared by the seeded emulsion polymerization of styrene [121]. The PMMA seed particles were initially prepared by the dispersion polymerization of MMA by using AIBN as the initiator. In this polymerization, poly(7V-vinyl pyrolli-done) and methyl tricaprylyl ammonium chloride were used as the stabilizer and the costabilizer, respectively, in the methanol medium. Seed particles were swollen with styrene monomer in a medium comprised of seed particles, styrene, water, poly(7V-vinyl pyrollidone), Polywet KX-3 and aeorosol MA emulsifiers, sodium bicarbonate, hydroquinone inhibitor, and azobis(2-methylbu-... 

MAIs may also be formed free radically when all azo sites are identical and have, therefore, the same reactivity. In this case the reaction with monomer A will be interrupted prior to the complete decomposition of all azo groups. So, Dicke and Heitz [49] partially decomposed poly(azoester)s in the presence of acrylamide. The reaction time was adjusted to a 37% decomposition of the azo groups. Surface active MAIs (M, > 10 ) consisting of hydrophobic poly(azoester) and hydrophilic poly(acrylamide) blocks were obtained (see Scheme 22) These were used for emulsion polymerization of vinyl acetate—in the polymerization they act simultaneously as emulsifiers (surface activity) and initiators (azo groups). Thus, a ternary block copolymer was synthesized fairly elegantly. 

MAI composed of PAIE for application to emulsifiers, drug carriers, and ion-exchange resins [60,61]. Poly(per-fluoropropyleneglycol)-b-poly(acrylic acid) was synthesized initiated with an MPI having fluoroalkyl group in the main chain [62]. It was soluble to water, ethanol, and THF, and showed water repellency, oil repellency, antifouling, and resistance to chemicals. 

Other common poly glycol-based antifoams include certain derivatives of polyethylene glycol (PEG), which are condensation polymers of ethylene glycol. An example is polyethylene glycol-8 dioleate. Apart from its antifoam properties, PEG-8 dioleate is also used in cooling water inhibitor formulations as a surface cleaner, in the formation of a corrosion-inhibiting surface film. Additionally, it is employed as an oil-soluble emulsifier for other defoamer chemistries. 

A related technique involves incorporation of monofunctional poly(etliylene oxide) chains as nonionic, internal emulsifier groups. Even PMDI can be dispersed in water using this nonionic method (Scheme 4.24). High-molecular-weight (ca. 2000 g/m) monols are usually used which act as chain terminators and long, hydrophilic tails which function as an emulsifying agent. 

Emulsions containing a water-solubile herbicide salt and a herbicide soluble in an organic solvent are prepared by a mixture of water, dioctyl phthalate, and isophorone. In this case ethoxylated poly ary lphenol phosphate neutralized with triethanolamine and ethoxylated acid phosphoric acid esters is used as emulsifier [231],... 

Emulsion polymerization is the most important process for production of elastic polymers based on butadiene. Copolymers of butadiene with styrene and acrylonitrile have attained particular significance. Polymerized 2-chlorobutadiene is known as chloroprene rubber. Emulsion polymerization provides the advantage of running a low viscosity during the entire time of polymerization. Hence the temperature can easily be controlled. The polymerizate is formed as a latex similar to natural rubber latex. In this way the production of mixed lattices is relieved. The temperature of polymerization is usually 50°C. Low-temperature polymerization is carried out by the help of redox systems at a temperature of 5°C. This kind of polymerization leads to a higher amount of desired trans-1,4 structures instead of cis-1,4 structures. Chloroprene rubber from poly-2-chlorbutadiene is equally formed by emulsion polymerization. Chloroprene polymerizes considerably more rapidly than butadiene and isoprene. Especially in low-temperature polymerization emulsifiers must show good solubility and... 

Surfactants which contain carboxylic acid ester or amide chains with terminal phosphonic acid groups are prepared from polyhydroxystearic acid or poly-caprolactone. Such reaction products are useful as dispersants, emulsifiers, and, in some cases, bactericides, disinfectants, and antiseptics see Sec. III.C.9 [69]. 

Hydrosilation reactions have been one of the earlier techniques utilized in the preparation of siloxane containing block copolymers 22,23). A major application of this method has been in the synthesis of polysiloxane-poly(alkylene oxide) block copolymers 23), which find extensive applications as emulsifiers and stabilizers, especially in the urethane foam formulations 23-43). These types of reactions are conducted between silane (Si H) terminated siloxane oligomers and olefinically terminated poly-(alkylene oxide) oligomers. Consequently the resulting system contains (Si—C) linkages between different segments. Earlier developments in the field have been reviewed 22, 23,43> Recently hydrosilation reactions have been used effectively by Ringsdorf 255) and Finkelmann 256) for the synthesis of various novel thermoplastic liquid crystalline copolymers where siloxanes have been utilized as flexible spacers. Introduction of flexible siloxanes also improved the processibility of these materials. 

Anionic emulsifiers, such as alkali salts of fatty acids, can be applied in anionic latices. Are particularly important as wetting and foaming agents in latex technology. Poly(glycol) ethers act as nonionogenic emulsifiers. 

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