Solubility amorphous polymers

White, hygroscopic, amorphous polymer. Soluble in water up to 10%. pH of 1% saline soln 5-9. Stable in soln and when autoclaved. Polymers with mol wt of 5000-10,000 have LDh i.v. in mice of 25-40 mg/kg. Ref Kimura et at., Toxicol Appl. Pharmacol. 1, 185 (1959), therap cat Heparin antagonist. 

The quinoxalline polymers, possessing higher glassing and softening temperatures and better mechanical properties compared to initial polymers, have been produced by means of interaction of polyester-a-diketones with a-phenylenediamine at 23 °C in m-cresol. Polyquinoxa-lines are amorphous polymers, soluble in chlorinated, amide and phenol dissolvents with Tiiini 0.4-0.6 deciliter/gram (25 °C, in N-methylpirroly-done of 0.5 gram/deciliter). 

Generally, linear polyoxazolides are amorphous polymers soluble in DMF at room temperature and having softening points between 150 and 200 C (Table 1). Herweh and Whitmore, confirmed the non-crystalline character of their poljrmer by x-ray diffraction studies. They concluded that crystallinity in polyoxazolidones is inhibited by their irregular chain structure, which arises from the presence of both 4- and 5-oxazolidone ring isomers. 

Solubility and Solvent Resistance. The majority of polycarbonates are prepared in methylene chloride solution. Chloroform, i7j -l,2-dichloroethylene, yy -tetrachloroethane, and methylene chloride are the preferred solvents for polycarbonates. The polymer is soluble in chlorobenzene or o-dichlorobenzene when warm, but crystallization may occur at lower temperatures. Methylene chloride is most commonly used because of the high solubiUty of the polymer (350 g/L at 25°C), and because this solvent has low flammabiUty and toxicity. Nonhalogenated solvents include tetrahydrofuran, dioxane, pyridine, and cresols. Hydrocarbons (qv) and aUphatic alcohols, esters (see Esters, organic), or ketones (qv) do not dissolve polycarbonates. Acetone (qv) promotes rapid crystallization of the normally amorphous polymer, and causes catastrophic failure of stressed polycarbonate parts. 

Structure and Crystallinity. The mechanical—optical properties of polycarbonates are those common to amorphous polymers. The polymer may be crystallized to some degree by prolonged heating at elevated temperature (8 d at 180°C) (16), or by immersion ia acetone (qv). Powdered amorphous powder appears to dissolve partially ia acetone, initially becoming sticky, then hardening and becoming much less soluble as it crystallizes. Enhanced crystallization of polycarbonate can also be caused by the presence of sodium phenoxide end groups (17). 

If 8j and 82 are identical then AH will be zero and so AF is bound to be negative and the compounds will mix. Thus the intuitive arguments put forward in Section 5.3 concerning the solubility of amorphous polymers can be seen to be consistent with thermodynamical treatment. The above discussion is, at best, an oversimplification of thermodynamics, particularly as applied to solubility. Further information may be obtained from a number of authoritative sources." ... 

The polymer, being amorphous, is soluble in solvents of similar solubility parameter, grades with low residual acetate being dissolved in solvents of solubility parameter between 19.8 and 22 MPa. ... 

As may be expected of an amorphous polymer in the middle range of the solubility parameter table, poly(methyl methacrylate) is soluble in a number of solvents with similar solubility parameters. Some examples were given in the previous section. The polymer is attacked by mineral acids but is resistant to alkalis, water and most aqueous inorganic salt solutions. A number of organic materials although not solvents may cause crazing and cracking, e.g. aliphatic alcohols. 

Of the instances of so-called solvent cracking of amorphous polymers known to the author, the liquid involved is not usually a true solvent of the polymer but instead has a solubility parameter on the borderline of the solubility range. Examples are polystyrene and white spirit, polycarbonate and methanol and ethyl acetate with polysulphone. The propensity to solvent stress cracking is however far from predictable and intending users of a polymer would have to check on this before use. 

These ideas might be used to explain the interesting results obtained recently by Williams et al.53 These workers observed formation of crystalline polystyrene when the reaction was initiated by triphenyl methyl potassium (or some other potassium metallo-organic compounds) in a hexane solution, but an amorphous polymer was formed in benzene. They point out that the catalyst is soluble in benzene but insoluble in hexane, and suggest that the heterogeneity of the catalyst is responsible for the results. Although this might be the case, an alternative explanation could be advanced.42 1... 

Aprotic polar solvents have to be used for several reasons. They are often good solvents for both monomers (including phenolates) and amorphous polymers. In addition, they can also stabilize the Meisenheimer intermediates. Common aprotic polar solvents, such as DMSO, /V,/V-dimcthyl acetamide (DMAc), DMF, N-methyl pyrrolidone (NMP), and cyclohexylpyrrolidone (CHP) can be used. Under some circumstances, very high reaction temperature and boiling point solvents such as sulfolane and diphenyl sulfone (DPS) have to be used due to the poor reactivity of the monomers or poor solubility of the resulting, possibly semicrystalline polymers, as in the PEEK systems. 

The curves of Figs. 133 and 134 may be regarded as plots of solubilities against temperature. It must be borne in mind however, that the dissolved phase is interspersed with the crystalline phase when polymer is present in excess of its solubility limit. Even in the more dilute solutions from which the crystalline polymer may settle out, the precipitate will contain some amorphous polymer and diluent. In short, these curves are useful primarily in defining the maximum amount of polymer which may be totally dissolved as a function of the temperature. 

The transition between crystalline and amorphous polymers is characterized by the so-called glass transition temperature, Tg. This important quantity is defined as the temperature above which the polymer chains have acquired sufficient thermal energy for rotational or torsional oscillations to occur about the majority of bonds in the chain. Below 7"g, the polymer chain has a more or less fixed conformation. On heating through the temperature Tg, there is an abrupt change of the coefficient of thermal expansion (or), compressibility, specific heat, diffusion coefficient, solubility of gases, refractive index, and many other properties including the chemical reactivity. 

The solubility parameter concept predicts the heat of mixing liquids and amorphous polymers. It has been experimentally found that generally any nonpolar amorphous polymer will dissolve in a liquid or mixture of liquids having a solubility parameter that generally does not differ by more than 1.8 (cal/cc) /. The Hildebrand (H) is preferred over these complex units, giving as a general difference 1.8 H. 

Amorphous polymers are characterized by the following properties They are transparent and very often soluble in common organic solvents at room temperature. The following amorphous polymers have gained industrial importance as thermoplastic materials polyfvinyl chloride), polystyrene, polyfmethyl methacrylate), ABS-polymers, polycarbonate, cycloolefine copolymers, polysulfone, poly( ether sulfone), polyfether imide). 

Amorphous polymers dissolve much easier than crystalline ones. The latter are often soluble at elevated temperatmes only, i.e., near the crystallite melting point T. ... 

The metallorganic compounds (I, II) employed in presence of a heterogeneous phase containing an amorphous compound of a low-valency, strongly electropositive transition metal, generally polymerize a-olefins to amorphous polymers. In a similar fashion, the soluble reaction products of such metallorganic compounds with compounds of transition metals, chemisorbed on amorphous substrates, polymerize a-olefins to amorphous polymers 6, 9). 

Crystalline polymers are much less soluble than amorphous polymers at temperatures below the melting point (Tm). Cross-linked polymers may swell but will not dissolve. 

He also showed that the size of the gas molecule is an important factor and that the solubility coefficient S of gases in amorphous polymers can be calculated from the following expression, which relates the critical temperature Tcl and boiling point Tb ... 

The principal polyolefins are low-density polyethylene (ldpe), high-density polyethylene (hope), linear low-density polyethylene (lldpe), polypropylene (PP), polyisobutylene (PIB), poly-1-butene (PB), copolymers of ethylene and propylene (EP), and proprietary copolymers of ethylene and alpha olefins. Since all these polymers are aliphatic hydrocarbons, the amorphous polymers are soluble in aliphatic hydrocarbon solvents with similar solubility parameters. Like other alkanes, they are resistant to attack by most ionic and most polar chemicals their usual reactions are limited to combustion, chemical oxidation, chlorination, nitration, and free-radical reactions. 

They are atactic amorphous polymers which have good light transparency (92%) and yield transparent moldings and films. As was noted for polyalkyl acrylates, the solubility parameters decrease as the size of the alkyl groups increases. The flexibility also increases as one goes from polymethyl methacrylate (PMMA) to polyaryl methacrylate and then decreases as the size of the alkyl group is further increased. 

These products are produced by the reaction of partially hydrolyzed PVAc with aldehydes. The acetal rings on these random amorphous polymer chains restrict flexibility and increase the heat deflection temperature to a value higher than that of PVAc. The heat deflection temperature of polyvinyl formal is about 90 C and is dependent on the specific composition of this complex polymer. Because of the presence of residual hydroxyl groups, commercial polyvinyl formal has a water absorption of about 1%. Polyvinyl formal has a Tg of 10S . It has a solubility parameter of about 10 H and is soluble in solvents with similar solubility parameters, such as acetone. 

Like dissolves like, and this is true with both polymers and smaller molecules. Thus linear amorphous polymers with nonpolar groups are typically soluble in nonpolar solvents with solubility parameter values within 1.8 H of that of the polymer. Thus polyisobutylene (PIB) is soluble in hot lubricating oils, and small amounts of high-molecular-weight PIB are used as viscosity improvers. 

All the synthesised polyimides are amorphous polymers with Tg in the range 223-320 °C, which is typical for flexible-chain polyimides [70], and their lie in the range 350 39 °C (Table 5.13). The polyimides are soluble (Table 5.13), the polymers based on the dianhydride of 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)-propane showing the highest solubility. 

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