Polyethylene solubilities

The informadon from this example tells us that 21,500 molecular weight polymer does not dissolve completely in ethylene, and a top phase and a bottom phase are formed. When the vessel is cooled (by the blast of cold air), both the phases are, of course, cooled. The example does not say if during the subsequent ethylene blowdown step any polyethylene escapes. However, at the cooled condidons, polyethylene solubility in ethylene is virtually nil and, therefore, we suggest that the aggregates of polyethylene are formed during the cooling step. The description of the polyethylene at the bottom of the vessel as a fused mass indicates that most of the ethylene had left the polyethylene before it solidified. 

In a classic 1978 paper [5,6], L.L. Bohm reported on the experimental parameters needed to establish steady-state polymerization conditions in order to eliminate monomer transport phenomena from the experimental results. As pointed out by Bohm, suspension or slurry polymerization takes place if the polymerization temperature is lower than the polyethylene solubility temperature and, therefore, the semicrystalline polymer precipitates from the suspension medium as the polymerization proceeds. The important physical process is the mass transfer of ethylene, comonomer and hydrogen (chain transfer reagent used to control polymer molecular weight) from the gas phase through the suspension medium and into the growing polymer particle to the active site. In order to obtain correct kinetic results, concentration gradients and temperature gradients within the polymer particle need to be removed from the polymerization process to achieve the necessary steady-state polymerization conditions. 

Although Pd is cheaper than Rh and Pt, it is still expensive. In Pd(0)- or Pd(ll)-catalyzed reactions, particularly in commercial processes, repeated use of Pd catalysts is required. When the products are low-boiling, they can be separated from the catalyst by distillation. The Wacker process for the production of acetaldehyde is an example. For less volatile products, there are several approaches to the economical uses of Pd catalysts. As one method, an alkyldi-phenylphosphine 9, in which the alkyl group is a polyethylene chain, is prepared as shown. The Pd complex of this phosphine has low solubility in some organic solvents such as toluene at room temperature, and is soluble at higher temperature[28]. Pd(0)-catalyzed reactions such as an allylation reaction of nucleophiles using this complex as a catalyst proceed smoothly at higher temperatures. After the reaction, the Pd complex precipitates and is recovered when the reaction mixture is cooled. 

Margarine and butter contain fat plus water and water-soluble ingredients, eg, salt and milk soHds that impart flavor and color to the product. Generally these products are distributed at refrigerated temperatures to retain their quaHty. Greaseproof packaging, such as polyethylene-coated paperboard, aluminum foil/paper, parchment paper wraps, and polypropylene tubs, is used for butter and margarine (see Dairy substitutes). 

Docusate Calcium. Dioctyl calcium sulfosuccinate [128-49-4] (calcium salt of l,4-bis(2-ethylhexyl)ester butanedioic acid) (11) is a white amorphous soHd having the characteristic odor of octyl alcohol. It is very slightly soluble in water, and very soluble in alcohol, polyethylene glycol 400, and com oil. It may be prepared directly from dioctyl sodium sulfo succinate dissolved in 2-propanol, by reaction with a methan olic solution of calcium chloride. 

LiAlH is soluble in ethers, 35-40 g/100 g diethyl ether at 25°C. Solubihty in THF, the other common solvent for LiAlH, is 13 g/100 g at 25°C. Polyethylene glycol diaLkyl ethers are also good solvents. 

Flexographic Inks. Fluorescent toners such as the Radiant GF, Lawter HVT, and Day-Glo HM and HMS Series toners are used in flexographic ink formulations. These products are soluble in blends of alcohol (80%) and ester solvents (20%) and are compatible with modifying materials such as nitroceUulose resins and acryHc solution polymers. Flexographic inks of this type are used most commonly to print products such as ceUophane and polyethylene film for packaging, and also to print paper products such as gift wrap and price labels. 

Solution Polymerization. Two solution polymerization technologies ate practiced. Processes of the first type utilize heavy solvents those of the second use molten PE as the polymerization medium (57). Polyethylene becomes soluble ia saturated C —hydrocarbons above 120—130°C. Because the viscosity of HDPE solutions rapidly iacrease with molecular weight, solution polymerization is employed primarily for the production of low mol wt resias. Solution process plants were first constmcted for the low pressure manufacture of PE resias ia the late 1950s they were later exteasively modified to make their operatioa economically competitive. 

Solubility. Cross-linking eliminates polymer solubiUty. Crystallinity sometimes acts like cross-linking because it ties individual chains together, at least well below T. Thus, there are no solvents for linear polyethylene at room temperature, but as it is heated toward its (135°C), it dissolves in a variety of aUphatic, aromatic, and chlorinated hydrocarbons. A rough guide to solubiUty is that like dissolves like, ie, polar solvents tend to dissolve polar polymers and nonpolar solvent dissolve nonpolar polymers. 

Functional derivatives of polyethylene, particularly poly(vinyl alcohol) and poly(acryLic acid) and derivatives, have received attention because of their water-solubility and disposal iato the aqueous environment. Poly(vinyl alcohol) is used ia a wide variety of appHcations, including textiles, paper, plastic films, etc, and poly(acryLic acid) is widely used ia detergents as a builder, a super-absorbent for diapers and feminine hygiene products, for water treatment, ia thickeners, as pigment dispersant, etc (see Vinyl polymers, vinyl alcohol polymers). 

Figures 4 and 5 show how the diffusion coefficient and solubility coefficient vary for a series of linear esters in low density polyethylene film. The trends are generally tme for other permeants in other films. As the size of the permeant increases, the diffusion coefficient decreases and the solubility coefficient increases. Since the increase in solubility coefficient is larger than the decrease in the diffusion coefficient, the permeability actually increases as the permeant size increases.

Fig. 5. Solubility coefficient at 30°C versus boiling point of ester in a low density polyethylene film (18). For unit conversion see equation 6.

These siUca-supported catalysts demonstrate the close connections between catalysis in solutions and catalysis on surfaces, but they are not industrial catalysts. However, siUca is used as a support for chromium complexes, formed either from chromocene or chromium salts, that are industrial catalysts for polymerization of a-olefins (64,65). Supported chromium complex catalysts are used on an enormous scale in the manufacture of linear polyethylene in the Unipol and Phillips processes (see Olefin polymers). The exact stmctures of the surface species are still not known, but it is evident that there is a close analogy linking soluble and supported metal complex catalysts for olefin polymerization. 

The process yields a random, completely soluble polymer that shows no evidence of crystallinity of the polyethylene type down to —60°C. The polymer backbone is fully saturated, making it highly resistant to ozone attack even in the absence of antiozonant additives. The fluid resistance and low temperature properties of ethylene—acryUc elastomers are largely a function of the methyl acrylate to ethylene ratio. At higher methyl acrylate levels, the increased polarity augments resistance to hydrocarbon oils. However, the decreased chain mobiUty associated with this change results in less fiexibihty at low temperatures. 

Water-soluble polymers and polyelectrolytes (e.g., polyethylene glycol, polyethylene imine polyacrylic acid) have been used success-hilly in protein precipitations, and there has been some success in affinity precipitations wherein appropriate ligands attached to polymers can couple with the target proteins to enhance their aggregation. Protein precipitation can also be achieved using pH adjustment, since proteins generally exhibit their lowest solubility at their isoelectric point. Temperature variations at constant salt concentration allow for frac tional precipitation of proteins. 

Polypropylene has a chemical resistance about the same as that of polyethylene, but it can be used at 120°C (250°F). Polycarbonate is a relatively high-temperature plastic. It can be used up to 150°C (300°F). Resistance to mineral acids is good. Strong alkalies slowly decompose it, but mild alkalies do not. It is partially soluble in aromatic solvents and soluble in chlorinated hydrocarbons. Polyphenylene oxide has good resistance to ahphatic solvents, acids, and bases but poor resistance to esters, ketones, and aromatic or chlorinated solvents. 

There are thus no solvents at room temperature for polyethylene, polypropylene, poly-4 methylpent-l-ene, polyacetals and polytetrafluoroethylene. However, as the temperature is raised and approaches F , the FAS term becomes greater than AH and appropriate solvents become effective. Swelling will, however, occur in the amorphous zones of the polymer in the presence of solvents of similar solubility parameter, even at temperatures well below T. ... 

In the case of crystalline polymers better results are obtained using an amorphous density which can be extrapolated from data above the melting point, or from other sources. In the case of polyethylene the apparent amorphous density is in the range 0.84-0.86 at 25°C. This gives a calculated value of about 8.1 for the solubility parameter which is still slightly higher than observed values obtained by swelling experiments. 

Hence polyethylene will be more permeable to liquids of similar solubility parameter, e.g. hydrocarbons, than to liquids of different solubility parameter but of similar size. The permeabilities of a number of polymers to a number of gases are given the Table 5.77. ... 

Since polyethylene is a crystalline hydrocarbon polymer incapable of specific interaction and with a melting point of about 100°C, there are no solvents at room temperature. Low-density polymers will dissolve in benzene at about 60°C but the more crystalline high-density polymers only dissolve at temperatures some 20-30°C higher. Materials of similar solubility parameter and low molecular weight will, however, cause swelling, the more so in low-density polymers Table 10.5). 

Poly(vinyl alcohol) is employed for a variety of purposes. Film cast from aqueous alcohol solution is an important release agent in the manufacture of reinforced plastics. Incompletely hydrolysed grades have been developed for water-soluble packages for bath salts, bleaches, insecticides and disinfectants. Techniques for making tubular blown film, similar to that used with polyethylene, have been developed for this purpose. Moulded and extruded products which combine oil resistance with toughness and flexibility are produced in the United States but have never become popular in Europe. 

Being a hydrocarbon with a solubility parameter of 18.6MPa - it is dissolved by a number of hydrocarbons with similar solubility parameters, such as benzene and toluene. The presence of a benzene ring results in polystyrene having greater reactivity than polyethylene. Characteristic reactions of a phenyl group such as chlorination, hydrogenation, nitration and sulphonation can all be performed with... 

Occasionally, water-soluble plastics are required. Poly(vinyl alcohol) is commonly the first to be considered but some cellulose ethers, polyethylene oxides, poly(vinyl pyrrolidone) and A-substituted polyamides are among many possible alternatives. 

These are all examples of soluble polymers. Combinations of soluble with insoluble polymers have also been reported. Polychloroprene or chlorosulfonated polyethylene was eombined with core-shell polymer particles to give an adhesive with improved cold impact resistance [33]. The fascinating chemistry of chlorosulfonated polyethylene in acrylic adhesives will be further discussed in the section on initiators. In many cases chlorosulfonated polyethylene is chemically attached to the acrylic matrix. 

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