Polymers tacky

These fixative polymers were designed to dissolve in these solvents. The critical performance parameters included polymer/solvent compatibility, polymer tackiness, polymer adhesion to the hairshaft, and the polymer s glass transition temperature (T ), which influenced the feel of the resin on the hair as well as its ability to hold the hair in a given style. The history of these fixative systems and polymers is well reviewed (110-117). 

A typical example is total monomers. 100 sodium stearate, 5 potassium persulfate, 0.3 lauryl mercaptan, 0.4 to 0.7 and water, 200 parts. In this formula, 75 parts of 1,3-butadiene and 25 parts of 4-methyl-2-vinylthiazole give 86% conversion to a tacky rubber-like copolymer in 15 hr at 45°C. The polymer contains 62% benzene-insoluble gel. Sulfur analysis indicates that the polymer contains 21 parts of combined 4-methyl-2-vinylthiazole (312). Butadiene alone in the above reaction normally requires 25 hr to achieve the same conversion, thus illustrating the acceleration due to the presence of 4-methyl-2-vinylthiazole. 

Polymers of different tacticity have quite different properties, especially in the solid state. One of the requirements for polymer crystallinity is a high degree of microstructural regularity to enable the chains to pack in an orderly manner. Thus atactic polypropylene is a soft, tacky substance, whereas both isotactic and syndiotactic polypropylenes are highly crystalline. 

Below T polymers are stiff, hard, britde, and glass-like above if the molecular weight is high enough, they are relatively soft, limp, stretchable, and can be somewhat elastic. At even higher temperatures they flow and are tacky. Methods used to determine glass-transition temperatures and the reported values for a large number of polymers may be found in References 7—9. Values for the T of common acrylate homopolymers are found in Table 1. 

Mechanical and Thermal Properties. The first member of the acrylate series, poly(methyl acrylate), has fltde or no tack at room temperature it is a tough, mbbery, and moderately hard polymer. Poly(ethyl acrylate) is more mbberflke, considerably softer, and more extensible. Poly(butyl acrylate) is softer stiU, and much tackier. This information is quantitatively summarized in Table 2 (41). In the alkyl acrylate series, the softness increases through n-octy acrylate. As the chain length is increased beyond n-octy side-chain crystallization occurs and the materials become brittle (42) poly( -hexadecyl acrylate) is hard and waxlike at room temperature but is soft and tacky above its softening point. 

Poly(vinyhdene chloride) (PVDC) film has exceUent barrier properties, among the best of the common films (see Barrier polymers). It is formulated and processed into a flexible film with cling and tacky properties that make it a useful wrap for leftovers and other household uses. As a component in coatings or laminates it provides barrier properties to other film stmctures. The vinyUdene chloride is copolymerized with vinyl chloride, alkyl acrylates, and acrylonitrile to get the optimum processibUity and end use properties (see Vinylidene chloride monomer and polymers). 

In methacrylic ester polymers, the glass-transition temperature, is influenced primarily by the nature of the alcohol group as can be seen in Table 1. Below the the polymers are hard, brittle, and glass-like above the they are relatively soft, flexible, and mbbery. At even higher temperatures, depending on molecular weight, they flow and are tacky. Table 1 also contains typical values for the density, solubiHty parameter, and refractive index for various methacrylic homopolymers. 

A substantial fraction of commercially prepared methacrylic polymers are copolymers. Monomeric acryUc or methacrylic esters are often copolymerized with one another and possibly several other monomers. Copolymerization greatiy increases the range of available polymer properties. The aH-acryhc polymers tend to be soft and tacky the aH-methacryhc polymers tend to be hard and brittie. By judicious adjustment of the amount of each type of monomer, polymers can be prepared at essentially any desired hardness or flexibiUty. Small amounts of specially functionalized monomers are often copolymerized with methacrylic monomers to modify or improve the properties of the polymer directiy or by providing sites for further reactions. Table 9 lists some of the more common functional monomers used for the preparation of methacrylic copolymers. 

Adhesives. High concentration (>10%) solutions of poly(ethylene oxide) exhibit wet tack properties that are used in several adhesive appHcations. The tackiness disappears when the polymer dries and this property can be successfully utilized in appHcations that require adhesion only in moist conditions. PEO is also known to form solution complexes with several phenoHc and phenoxy resins. Solution blends of PEO and phenoxy resins are known to exhibit synergistic effects, leading to high adhesion strength on aluminum surfaces. Adhesive formulations are available from the manufacturers. 

Another technique to reduce the problems caused by stickies is to use additives to reduce the tackiness of these particles. This prevents their later reagglomeration and attachment to paper machine surfaces. These additives are usually added to the pulper. The most common is talc (17) usually added to the pulper in repulpable bags. Emulsified talc is also sometimes added to the pulp just before the pulp encounters high shear. Organic polymers (18) such as a polyvinylpyrrohdinone (PVP) copolymer (19) have also been reported to reduce the tackiness of stickies. 

Tackifiers are used to increase the tackiness and the setting speed of adhesives. They increase tackiness by softening the poly(vinyl acetate) polymer in the wet and the dry adhesive film. Tackifiers are usually rosin or its derivatives or phenoHc resins. Other additives frequently needed for specific apphcation and service conditions are antifoams, biocides, wetting agents, and humectants. 

Stereoregular Polymerization. Chemists at GAF Corporation were first to suggest that stereoregularity or the lack thereof is responsible for both nontacky and crystalline or tacky and amorphous polymers generated from IBVE with BF2 0(C2H )2, depending on the reaction conditions (22,23). In addition, it was shown that the crystalline polymer is actually isotactic (24). Subsequentiy, the reaction conditions necessary to form such polymers have not only been demonstrated, but the stereoregular polymerization has been extended to other monomers, such as methyl vinyl ether (25,26). 

Particulate fillers are divided into two types, inert fillers and reinforcing fillers. The term inert filler is something of a misnomer as many properties may be affected by incorporation of such a filler. For example, in a plasticised PVC compound the addition of an inert filler will reduce die swell on extrusion, increase modulus and hardness, may provide a white base for colouring, improve electrical insulation properties and reduce tackiness. Inert fillers will also usually substantially reduce the cost of the compound. Amongst the fillers used are calcium carbonates, china clay, talc, and barium sulphate. For normal uses such fillers should be quite insoluble in any liquids with which the polymer compound is liable to come into contact. 

Another major area of use is in the field of adhesives. The main attractions of the material are the absence of a need for mastication, easy solvation of the polymer, which is supplied in a crumb form, the production of low-viscosity solutions and high joint strength. In conjunction with aromatic resins they are used for contact adhesives whilst with aliphatic resin additives they are used for permanently tacky pressure-sensitive adhesives. In addition to being applied from solution they may be applied as a hot melt. 

Barquins, M. and Maugis, D., Tackiness of elastomers. J. Adhes., 13, 53-65 (1981). Creton, C. and Lakrout, H., Micromechanics of flat-probe adhesion tests of soft vi.scoelas-tic polymer films. J. Polym. Sci. B Polym. Phys., 38(7), 965-979 (2000). 

While there are a large number of elastomers that can be formulated into pressure sensitive adhesives, the following list is intended to focus on commercially significant materials. Two subsets are differentiated in Table 1 those polymers that can be inherently tacky, and those that require modification with tackifiers to meet the Tg and modulus criteria to become pressure sensitive. 

A significant step towards commercial success came with a discovery in the late 1950s by E. Ulrich at 3M when he found that copolymerization of hydrogen bonding monomers, like acrylic acid with alkyl acrylates resulted in cohesively strong, yet tacky materials [63]. Since then, newer developments in such areas as polymer crosslinking, and the synthesis and copolymerization of new monomers, have led to a rapid penetration of acrylics throughout the PSA industry. 

Among the different pressure sensitive adhesives, acrylates are unique because they are one of the few materials that can be synthesized to be inherently tacky. Indeed, polyvinylethers, some amorphous polyolefins, and some ethylene-vinyl acetate copolymers are the only other polymers that share this unique property. Because of the access to a wide range of commercial monomers, their relatively low cost, and their ease of polymerization, acrylates have become the dominant single component pressure sensitive adhesive materials used in the industry. Other PSAs, such as those based on natural rubber or synthetic block copolymers with rubbery midblock require compounding of the elastomer with low molecular weight additives such as tackifiers, oils, and/or plasticizers. The absence of these low molecular weight additives can have some desirable advantages, such as ... 

For some applications, such as for repulpable type PSAs, it may be advantageous to incorporate high levels of acrylic acid because this makes the polymer more hydrophilic. At the same time, high levels of acid also improve the water-dispersibility of the adhesive, especially at higher pH where the acid groups are converted to the more water-soluble neutralized salt form. Since the high level of acid increases the of the resulting polymer, a non-tacky material results. To make the adhesive pressure sensitive, the polymer can be softened with water-dispersible or soluble plasticizers, such as polyethers [68]. 

Acrylic polymers have the advantage that they can be formulated to be inherently tacky. However, for certain applications it may be desirable to adjust the rheological properties of the PSA beyond what can be obtained by selecting the right polymer composition and crosslink density. 

Other polymers used in the PSA industry include synthetic polyisoprenes and polybutadienes, styrene-butadiene rubbers, butadiene-acrylonitrile rubbers, polychloroprenes, and some polyisobutylenes. With the exception of pure polyisobutylenes, these polymer backbones retain some unsaturation, which makes them susceptible to oxidation and UV degradation. The rubbers require compounding with tackifiers and, if desired, plasticizers or oils to make them tacky. To improve performance and to make them more processible, diene-based polymers are typically compounded with additional stabilizers, chemical crosslinkers, and solvents for coating. Emulsion polymerized styrene butadiene rubbers (SBRs) are a common basis for PSA formulation [121]. The tackified SBR PSAs show improved cohesive strength as the Mooney viscosity and percent bound styrene in the rubber increases. The peel performance typically is best with 24—40% bound styrene in the rubber. To increase adhesion to polar surfaces, carboxylated SBRs have been used for PSA formulation. Blends of SBR and natural rubber are commonly used to improve long-term stability of the adhesives. 

Solvent-borne adhesives. Although the NR polymer is inherently tacky, tack-ifying resins are generally added to improve bonding to polar surfaces. Because the solids content in these adhesives is lower than 35 wt%, they are not suitable for gap filling. The quick-grab (cements) adhesives are particular because they contain about 65 wt% rubber, and set within a few seconds under finger pressure. 

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