Poly glycol ethers

Title Amorphous Poly ether Glycols Based on bis-Substituted Oxetane and Tetrahydrofuran Monomers... 

POLYEPPiERS - PEPRAPiYDROFURAN AND OXETANE POLYPOUS] (Vol 19) Poly(tetramethylene ether) glycol... 

Halex rates can also be increased by phase-transfer catalysts (PTC) with widely varying stmctures quaternary ammonium salts (51—53) 18-crown-6-ether (54) pytidinium salts (55) quaternary phosphonium salts (56) and poly(ethylene glycol)s (57). Catalytic quantities of cesium duoride also enhance Halex reactions (58). 

Although synthetic lubrication oil production amounts to only about 2% of the total market, volume has been increasing rapidly (67). Growth rates of the order of 20% per year for poly( a-olefin)s, 10% for polybutenes, and 8% for esters (28) reflect increasing automotive use and these increases would accelerate if synthetics were adopted for factory fill of engines by automotive manufacturers. The estimated production of poly( a-olefin)s for lubricants appears to be approximately 100,000 m /yr, esters 75,000, poly(alkylene glycol)s 42,000, polybutenes 38,000, phosphates 20,000, and dialkyl benzene 18,000 (28,67). The higher costs reflected in Table 18 (18,28) have restricted the volume of siUcones, chlorotrifluoroethylene, perfluoroalkylpolyethers, and polyphenyl ethers. 

The most important tetrahydrofuran polymers are the hydroxy-terrninated polymers, that is, the a,C0-poly(tetramethylene ether) glycols used commercially to manufacture polyurethanes and polyesters (see Urethane polymers Polyesters, thermoplastic). 

A number of papers and patents describe polymerization processes to poly(tetramethylene ether) glycols having a narrow molecular weight distribution = 1.2—1.4). In principle, this can be achieved by having all chains grow quickly at one time, either by high temperature initiation (33)... 

Eig. 1. Viscosities (Brookfield) of poly(tetramethylene ether) glycol of the following molecular weights A, 2000 (Terathane 2000) B, 1000 (Terathane 1000) ... 

Table 3. Selected Thermal Properties of Poly(Tetramethylene Ether) Glycols ...

Poly(tetramethylene ether) glycols were found to have low oral toxicity in animal tests. The approximate lethal oral dose, LD q, for Terathane 1000 has been found to be greater than 11,000 mg/kg (272). No adverse effects on inhalation have been observed. The polymer glycols are mild skin and eye irritants, and contact with skin, eyes, and clothing should be avoided. Goggles and gloves are recommended. In case of contact with the skin, wash thoroughly with water and soap. If swallowed, no specific intervention is indicated, because the compounds are not hazardous. However, a physician should be consulted (260). 

Natural Products. Many natural products, eg, sugars, starches, and cellulose, contain hydroxyl groups that react with propylene oxide. Base-cataly2ed reactions yield propylene glycol monoethers and poly(propylene glycol) ethers (61—64). Reaction with fatty acids results ia a mixture of mono- and diesters (65). Cellulose fibers, eg, cotton (qv), have been treated with propylene oxide (66—68). 

Reactive (unsaturated) epoxy resins (qv) are reaction products of multiple glycidyl ethers of phenoHc base polymer substrates with methacrylic, acryhc, or fumaric acids. Reactive (unsaturated) polyester resins are reaction products of glycols and diacids (aromatic, aUphatic, unsaturated) esterified with acryhc or methacrylic acids (see POLYESTERS,unsaturated). Reactive polyether resins are typically poly(ethylene glycol (600) dimethacrylate) or poly(ethylene glycol (400) diacrylate) (see PoLYETPiERs). 

Polyether Polyols. Polyether polyols are addition products derived from cyclic ethers (Table 4). The alkylene oxide polymerisation is usually initiated by alkah hydroxides, especially potassium hydroxide. In the base-catalysed polymerisation of propylene oxide, some rearrangement occurs to give aHyl alcohol. Further reaction of aHyl alcohol with propylene oxide produces a monofunctional alcohol. Therefore, polyether polyols derived from propylene oxide are not truly diftmctional. By using sine hexacyano cobaltate as catalyst, a more diftmctional polyol is obtained (20). Olin has introduced the diftmctional polyether polyols under the trade name POLY-L. Trichlorobutylene oxide-derived polyether polyols are useful as reactive fire retardants. Poly(tetramethylene glycol) (PTMG) is produced in the acid-catalysed homopolymerisation of tetrahydrofuran. Copolymers derived from tetrahydrofuran and ethylene oxide are also produced. 

Choline is a strong base (pif = 5.06for0.0065-0.0403 Afsolutions ) (3). It crystallizes with difficulty and is usually known as a colorless deHquescent sympy hquid, which absorbs carbon dioxide from the atmosphere. Choline is very soluble in water and in absolute alcohol but insoluble in ether (4). It is stable in dilute solutions but in concentrated solutions tends to decompose at 100°C, giving ethylene glycol, poly(ethylene glycol), and trimetbylamine (5). 

When exposed to heat, cotton fabrics, like most substances, increase in temperature to an extent that is proportional to their specific heats. Altering the chemical composition of the fabrics such that large amounts of heat are absorbed and released in repeatable cycles of controllable temperature ranges produces fabrics that are described as temperature adaptable. The process insolubili2es poly(ethylene glycol)s cross-linked with methylolamides in the cotton fabric (78). As with flame-retardant cellulose, attachment is through an ether linkage to the cellulose at a relatively low DS. 

Liquid Third Phase. A third Hquid with coUoidal stmcture has been a known component in emulsions since the 1970s (22) for nonionic surfactants of the poly(ethylene glycol) alkylaryl ether type. It allows low energy emulsification (23) using the strong temperature dependence of the coUoidal association stmctures in the water—surfactant—hydrocarbon systems. 

Uses. Approximately 70% of the U.S. production is used to make poly(tetramethylene ether glycol) [25190-06-1] (PTMEG), also known as poly-THE, which is used in the production of urethane elastomers, polyurethane fibers (ether-based spandex), and copolyester—ether elastomers. PTMEG is also the fastest growing use (see PoLYETPiERS, TETRAHYDROFURAn). The remaining production is used as a solvent for the manufacture of poly(vinyl chloride) cements and coating, precision magnetic tape, a reaction solvent in the production of pharmaceuticals, and other miscellaneous uses. 

With Phenols. The 2-hydroxylethyl aryl ethers are prepared from the reaction of ethylene oxide with phenols at elevated temperatures and pressures (78,79). 2-Phenoxyethyl alcohol is a perfume fixative. The water-soluble alkylphenol ethers of the higher poly(ethylene glycol)s are important surface-active agents. They are made by adding ethylene oxide to the alkylphenol at ca 200°C and 200—250 kPa (>2 atm), using sodium acetate or... 

Chemical Designations - Synonyms Cellosolve Dowanol EE 2-Ethoxyethanol Ethylene Glycol Ethyl Ether Glycol Monoethyl ether Poli-Solv EE Chemical Formula HOCHjCH OCHjCHj. Observable Characteristics - Physical State (as shipped) Liquid Color Colorless Odor Sweetish mild, pleasant, ethereal. 

Example 2. Two-Shot Cast Elastomer (Prepolymer Method). Synthesis of polyurethane elastomers via the prepolymer method is challenging and requires especial attention to details and techniques. This example is a relatively easy one, using a low-viscosity, 9.6% NCO MDI-based poly(tetramethylene ether) glycol prepolymer. It is adapted from the Bayer Product Information Bulletin for Baytec ME-090 prepolymer. 

Fakirov S and Gogeva T. Poly(ether ester)s based on poly(butylene terephthalate) and poly(ethylene oxide)glycols, 1. Makromol Chem, 1990, 191, 603-614. 

Deschamps AA, van Apeldoom AA, Hayen H, et al. In vivo and in vitro degradation of poly(ether ester) block copolymers based on poly(ethylene glycol) and poly (butylene terephthalate)[J]. Biomaterials, 2004, 25, 247-258. 

Polyphosphazenes sulfonates XIX with the anion covalently attached to the polymer are a new class of cation conductors that have been synthesized by Shriver [625]. They were obtained by reaction of Na0C2H4S03Na with an excess of polydichlorophosphazene in the presence of 15-crown-5, followed by the reaction of the partially substituted product with the sodium salt of poly(ethylene glycol methyl ether). The conductivity at 80 °C of the polymer with x=1.8, m=7.22 is 1.7x10 S cm This low conductivity can be attributed to an extensive ion pair formation between the sodium and sulfonate ions. 

Solubilization of a graft copolymer comprising a hydrophobic poly(dodecyl-methacrylate) backbone and hydrophilic poly(ethylene glycol) monomethyl ether side chains in water/AOT/cyclohexane w/o microemulsions was rationalized in terms of the backbone dissolved in the continuous apolar phase and the side chains entrapped within the aqueous micellar cores [189],... 

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