Copolymers viscosities

The most important properties of the matrix polymer are its chemical composition and melt viscosity. Copolymers have lower stiffness and higher impact strength than the homopolymer, which are transferred also to the composites. Products with Mgher modulus are usually prepared from homopolymers, while those subjected to dynamic loads during application are made from copolymers. Also the sequence distribution of the ethylene and propylene units is of importance, as... 

Branched polymers in solution also show concentration-dependent transitions in viscosity. Copolymers of poly(ethylene terephthalate-co-ethylene isophthalate) (P(ET-co-EI)) were prepared by the polycondensation reaction of an equimolar mixture of dimethyl terephthalate (DMT) and dimethyl isophthalate (DM1) in the presence of a 100% excess of ethylene glycol (EG) (Scheme 3.1). Chain branching was introduced into the polymer using a tri-functional anhydride or a tricarboxylate at a level of 1 -1.5 molar percent. The concentration dependence of viscosity for these polymers were Tjsp ... 

The major use of vinylpyrrohdinone is as a monomer in manufacture of poly(vinylpyrrohdinone) (PVP) homopolymer and in various copolymers, where it frequendy imparts hydrophilic properties. When PVP was first produced, its principal use was as a blood plasma substitute and extender, a use no longer sanctioned. These polymers are used in pharmaceutical and cosmetic appHcations, soft contact lenses, and viscosity index improvers. The monomer serves as a component in radiation-cured polymer compositions, serving as a reactive diluent that reduces viscosity and increases cross-linking rates (see... 

Polyacrylamides are used in many other oilfield appUcations. These include cement additives for fluid loss control in well cementing operations (127), viscosity control additives for drilling muds (128), and fracturing fluids (129). Copolymers [40623-73-2] of acrylamide and acrylamidomethylpropanesulfonic acid do not degrade with the high concentrations of acids used in acid fracturing. 

The properties of SAN resins depend on their acrylonittile content. Both melt viscosity and hardness increase with increasing acrylonittile level. Unnotched impact and flexural strengths depict dramatic maxima at ca 87.5 mol % (78 wt %) acrylonitrile (8). With increasing acrylonitrile content, copolymers show continuous improvements in barrier properties and chemical and uv resistance, but thermal stabiUty deteriorates (9). The glass-transition... 

SAN resins show considerable resistance to solvents and are insoluble in carbon tetrachloride, ethyl alcohol, gasoline, and hydrocarbon solvents. They are swelled by solvents such as ben2ene, ether, and toluene. Polar solvents such as acetone, chloroform, dioxane, methyl ethyl ketone, and pyridine will dissolve SAN (14). The interactions of various solvents and SAN copolymers containing up to 52% acrylonitrile have been studied along with their thermodynamic parameters, ie, the second virial coefficient, free-energy parameter, expansion factor, and intrinsic viscosity (15). 

The molecular weight of SAN can be easily determined by either intrinsic viscosity or size-exclusion chromatography (sec). Relationships for both multipoint and single point viscosity methods are available (18,19). Two intrinsic viscosity and molecular weight relationships for azeotropic copolymers have been given (20,21) ... 

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). 

Peifluorinated ethylene—piopjiene (FEP) lesin [25067-11-2] is a copolymer of tetiafluoioethylene [116-14-3] (TFE) and hexafluoiopiopylene [116-15-4] (HEP) thus its blanched stmctuie contains units of —CF2—CF2— and units of —CF2—CF(CF2)—. It retains most of the desirable characteristics of polytetrafluoroethylene (PTFE) but with a melt viscosity low enough for conventional melt processing. The introduction of hexafluoropropylene lowers the melting point of PTFE from 325°C to about 260°C. 

Hexafluoiopiopylene and tetiafluoioethylene aie copolymerized, with trichloiacetyl peroxide as the catalyst, at low temperature (43). Newer catalytic methods, including irradiation, achieve copolymerization at different temperatures (44,45). Aqueous and nonaqueous dispersion polymerizations appear to be the most convenient routes to commercial production (1,46—50). The polymerization conditions are similar to those of TFE homopolymer dispersion polymerization. The copolymer of HFP—TFE is a random copolymer that is, HFP units add to the growing chains at random intervals. The optimal composition of the copolymer requires that the mechanical properties are retained in the usable range and that the melt viscosity is low enough for easy melt processing. 

Hexafluoropropylene—tetrafluoroethylene copolymers are available in low melt viscosity, extmsion grade, intermediate viscosity, high melt viscosity, and as dispersions. The low melt viscosity (MV) resin can be injection molded by conventional thermoplastic molding techniques. It is more suitable for injection molding than other FEP resins (51). 

The polymerization is carried out at temperatures of 0—80°C in 1—5 h at a soHds concentration of 6—12%. The polymerization is terminated by neutralizing agents such as calcium hydroxide, calcium oxide, calcium carbonate, or lithium hydroxide. Inherent viscosities of 2-4 dL/g are obtained at 3,4 -dianiinodiphenyl ether contents of 35—50 mol %. Because of the introduction of nonlinearity into the PPT chain by the inclusion of 3,4 -dianiinodiphenyl ether kinks, the copolymer shows improved tractabiUty and may be wet or dry jet-wet spun from the polymerization solvent. The fibers are best coagulated in an aqueous equiUbrium bath containing less than 50 vol % of polymerization solvent and from 35 to 50% of calcium chloride or magnesium chloride. 

Styrenic block copolymers (SBCs) are also widely used in HMA and PSA appHcations. Most hot melt appHed pressure sensitive adhesives are based on triblock copolymers consisting of SIS or SBS combinations (S = styrene, I = isoprene B = butadiene). Pressure sensitive adhesives typically employ low styrene, high molecular weight SIS polymers while hot melt adhesives usually use higher styrene, lower molecular weight SBCs. Resins compatible with the mid-block of an SBC improves tack properties those compatible with the end blocks control melt viscosity and temperature performance. 

Table 9 compares the most important properties of substrate materials based on BPA-PC, PMMA, and CPO (three different products) (216,217). The future will prove if the current disadvantages of CPO against BPA-PC regarding warp, processibiUty (melt viscosity), and especially cost can be alleviated. CycHc polyolefins (CPO) and, especially cycloolefin copolymers (COC) (218) and blends of cycloolefin copolymers with suitable engineering plastics have the potential to be interesting materials for substrate disks for optical data storage. 

Butyl mbber, a copolymer of isobutjiene with 0.5—2.5% isoprene to make vulcanization possible, is the most important commercial polymer made by cationic polymerization (see Elastomers, synthetic-butyl rubber). The polymerization is initiated by water in conjunction with AlCl and carried out at low temperature (—90 to —100° C) to prevent chain transfer that limits the molecular weight (1). Another important commercial appHcation of cationic polymerization is the manufacture of polybutenes, low molecular weight copolymers of isobutylene and a smaller amount of other butenes (1) used in adhesives, sealants, lubricants, viscosity improvers, etc. 

Melt Viscosity. As shown in Tables 2 and 3, the melt viscosity of an acid copolymer increases dramatically as the fraction of neutralization is increased. The relationship for sodium ionomers is shown in Figure 4 (6). Melt viscosities for a series of sodium ionomers derived from an ethylene—3.5 mol % methacrylic acid polymer show that the increase is most pronounced at low shear rates and that the ionomers become increasingly non-Newtonian with increasing neutralization (9). The activation energy for viscous flow has been reported to be somewhat higher in ionomers than in related acidic... 

Polyoxymethylene Ionomers. Ionic copolymers have been prepared from trioxane and epichlorohydrin, followed by reaction with disodium thioglycolate (76). The ionic forces in these materials dismpt crystalline order and increase melt viscosity (see Acetalresins). 

The polyamides are soluble in high strength sulfuric acid or in mixtures of hexamethylphosphoramide, /V, /V- dim ethyl acetam i de and LiCl. In the latter, compHcated relationships exist between solvent composition and the temperature at which the Hquid crystal phase forms. The polyamide solutions show an abmpt decrease in viscosity which is characteristic of mesophase formation when a critical volume fraction of polymer ( ) is exceeded. The viscosity may decrease, however, in the Hquid crystal phase if the molecular ordering allows the rod-shaped entities to gHde past one another more easily despite the higher concentration. The Hquid crystal phase is optically anisotropic and the texture is nematic. The nematic texture can be transformed to a chiral nematic texture by adding chiral species as a dopant or incorporating a chiral unit in the main chain as a copolymer (30). 

Low molecular weight (1000—5000) polyacrylates and copolymers of acryflc acid and AMPS are used as dispersants for weighted water-base muds (64). These materials, 40—50% of which is the active polymer, are usually provided in a Hquid form. They are particularly useful where high temperatures are encountered or in muds, which derive most of their viscosity from fine drill soHds, and polymers such as xanthan gum and polyacrylamide. Another high temperature polymer, a sulfonated styrene maleic—anhydride copolymer, is provided in powdered form (65,66). AH of these materials are used in relatively low (ca 0.2—0.7 kg/m (0.5—2 lb /bbl)) concentrations in the mud. 

A hydrolyzed cereal soHd, predominately a hexasaccharide, is used in high pH lime muds for reducing the yield point and gel strength (67). This additive has been used in systems treated with both sodium hydroxide and potassium hydroxide in addition to other additives common to lime muds (68). A second viscosity-reducing additive used in lime muds is a graft copolymer of acryflc acid and calcium flgnosulfonate (69). Both of these materials are used at levels of 6—17 kg/m (2—6 lb /bbl). 

In low sohds muds, vinyl acetate—maleic anhydride copolymers were once used to extend or enhance the viscosity of bentonite suspensions (141). This function is largely performed by polyacrylamides. The vinyl acetate—maleic anhydride copolymers can also have a flocculating effect on drill sohds. Concentrations generally are quite low (0.14—0.57 kg/m (0.05—0.2 Ib/bbl)). 

Rosin, modified rosins, and derivatives are used in hot-melt adhesives. They are based primarily on ethylene—vinyl acetate copolymers. The rosin derivative is used in approximately a 1 1 1 concentration with the polymer and a wax. The resin provides specific adhesion to the substrates and reduces the viscosity at elevated temperatures, allowing the adhesive to be appHed as a molten material. 

Depending on the concentration, the solvent, and the shear rate of measurement, concentrated polymer solutions may give wide ranges of viscosity and appear to be Newtonian or non-Newtonian. This is illustrated in Eigure 10, where solutions of a styrene—butadiene—styrene block copolymer are Newtonian and viscous at low shear rates, but become shear thinning at high shear rates, dropping to relatively low viscosities beyond 10 (42). The... 

Fig. 10. Viscosity vs shear rate for solutions of a styrene—butadiene—styrene block copolymer (42). A represents cyclohexanone, where c = 0.248 g/cm (9-xylene, where c = 0.246 g/cm C, toluene, where c = 0.248 g/cm. Courtesy of the Society of Plastics Engineers, Inc.

Among the techniques employed to estimate the average molecular weight distribution of polymers are end-group analysis, dilute solution viscosity, reduction in vapor pressure, ebuUiometry, cryoscopy, vapor pressure osmometry, fractionation, hplc, phase distribution chromatography, field flow fractionation, and gel-permeation chromatography (gpc). For routine analysis of SBR polymers, gpc is widely accepted. Table 1 lists a number of physical properties of SBR (random) compared to natural mbber, solution polybutadiene, and SB block copolymer. 

---