OXYPROPYLENE

Several studies have demonstrated the successful incoriDoration of [60]fullerene into polymeric stmctures by following two general concepts (i) in-chain addition, so called pearl necklace type polymers or (ii) on-chain addition pendant polymers. Pendant copolymers emerge predominantly from the controlled mono- and multiple functionalization of the fullerene core with different amine-, azide-, ethylene propylene terjDolymer, polystyrene, poly(oxyethylene) and poly(oxypropylene) precursors [63,64,65,66,62 and 66]. On the other hand, (-CggPd-) polymers of the pearl necklace type were fonned via the periodic linkage of [60]fullerene and Pd monomer units after their initial reaction with thep-xy y ene diradical [69,70 and 71]. 

Wanka G, Floffman FI and Ulbrict W 1990 The aggregation behavior of poly-(oxyethylene)-poly(oxypropylene)-poly-(oxyethylene)-block copolymers in aqueous solutions Colloid Polym. Sc/. 268 101-17... 

Reaction of olefin oxides (epoxides) to produce poly(oxyalkylene) ether derivatives is the etherification of polyols of greatest commercial importance. Epoxides used include ethylene oxide, propylene oxide, and epichl orohydrin. The products of oxyalkylation have the same number of hydroxyl groups per mole as the starting polyol. Examples include the poly(oxypropylene) ethers of sorbitol (130) and lactitol (131), usually formed in the presence of an alkaline catalyst such as potassium hydroxide. Reaction of epichl orohydrin and isosorbide leads to the bisglycidyl ether (132). A polysubstituted carboxyethyl ether of mannitol has been obtained by the interaction of mannitol with acrylonitrile followed by hydrolysis of the intermediate cyanoethyl ether (133). 

Polyall lene Oxide Block Copolymers. The higher alkylene oxides derived from propjiene, butylene, styrene (qv), and cyclohexene react with active oxygens in a manner analogous to the reaction of ethylene oxide. Because the hydrophilic oxygen constitutes a smaller proportion of these molecules, the net effect is that the oxides, unlike ethylene oxide, are hydrophobic. The higher oxides are not used commercially as surfactant raw materials except for minor quantities that are employed as chain terminators in polyoxyethylene surfactants to lower the foaming tendency. The hydrophobic nature of propylene oxide units, —CH(CH2)CH20—, has been utilized in several ways in the manufacture of surfactants. Manufacture, properties, and uses of poly(oxyethylene- (9-oxypropylene) have been reviewed (98). 

Pluronic L62 is a poly(oxyethylene)—poly(oxypropylene)—poly(oxyethylene) copolymer marketed by BASF AG. 

If flammabiHty is an issue, Hquid chloroprene polymers (eg, Du Pont PB or Denki LCR-H-050) can be used. They cocure and, for that reason, are nonvolatile and nonextractable. They are particularly useful in hard compounds where they do not detract from physical properties as much as nonreactive plastici2ers (132,133). Methacrylate esters have been used as reactive plastici2ers (qv). Por example, hexa(oxypropylene)glycolmonomethacrylate can be used as a reactive plastici2er to enhance flex life without increasing hardness (134). 

The secondary hydroxyl groups of these poly(oxypropylene) glycol diols are less reactive than the primary hydroxyl groups of the earlier polyesters. At the time of the introduction of these polyethers, the catalysts then available were insufficiently powerful for one-shot processes to be practical and so these polymers have been used primarily in prepolymer processes. 

The most common non-crystallizing soft segment in urethane adhesives is based on poly(oxypropylene) polyols, shown in Table 2. Most non-crystalline soft... 

Most moisture-curing liquid adhesives utilize poly(oxypropylene) (PPG) polyols, as shown above. These raw materials produce among the lowest-viscosity prepolymers but may not have sufficient modulus at higher temperatures for some applications. A certain percentage of polyester polyols may also be utilized to boost performance, but these may cause a large increase in viscosity, and so they are more often used in conjunction with polyether polyols to provide a high-performance adhesive with workable viscosities. Poly(butadiene) polyols may be utilized for specific adhesion characteristics. 

Ethylene oxide capped poly(oxypropylene) diol, MW 2800 100... 

Polyesters and polycarbonate polyols show improved resistance to oxidative attack, compared with that of the polyethers. Stress relation studies run at 130°C, comparing a urethane based on a poly(oxypropylene) polyol and a urethane based on poly(butane adipate) polyol show that, after 60 h, the urethane based on PPG lost most of its strength, while the polyester retained most of its strength [83], Urethanes made from poly(butadiene) polyols are also susceptible to oxidation, but they show good resistance to air-oven aging with antioxidants present (see p. 290 in [45],... 

Chemical Name Poly (oxyethylene)-poly(oxypropylene)-poly (oxyethylene) Common Name Poloxalene... 

Nitriles react with alcohols in the presence of hydrochloric acid to form iminoester hydrochlorides, which are hydrolyzed to the esters (Pinner synthesis). Heitz and coworkers [21-23] published several fine papers on the polyazoester synthesis from the reaction of a series of poly(oxyethylene) glycol or poly(oxypropylene) glycol and AIBN in the presence of dry hydrochloric acid at 0-5°C according to Pinner synthesis. Condensation reactions of ACPC and dihydroxy terminated poly(oxy-ethylene) glycol yield polyazoesters [24,25]. 

At constant PBT/PTMO composition, when the molar mass of PTMO block is >2000, partial crystallization of the polyether phase leads to copolymer stiffening. The properties of polyesterether TPEs are not dramatically different when PTMO is replaced by polyethers such as poly(oxyethylene) (PEO) or poly(oxypropylene). PEO-based TPEs present higher hydrophilicity, which may be of interest for some applications such as waterproof breathable membranes but which also results in much lower hydrolysis resistance. Changing PBT into a more rigid polymer by using 2,6-naphthalene dicarboxylic acid instead of terephthalic acid results in compounds that exhibit excellent general properties but poorer low-temperature stiffening characteristics. 

Porous membranes have been prepared by leaching an additive from films and tubes of PCL (64,72). The procedure involves extrusion or casting blends of PCL and Pluronic F68, the latter being an FDA-approved oxyethylene-co-oxypropylene triblock copolymer. Treatment of the phase-separated blend with aqueous acetone or aqueous alcohols causes both swelling of the polymer and extraction of the Pluronic F68. The induced pore size and void volume may be controlled by the time, temperature, and solvent composition. 

Prud homme, RK Wu, G Schneider, DK, Structure and Rheology Studies of Poly(oxyethy-lene-oxypropylene-oxyethylene) Aqueous Solution, Langmuir 12, 4651, 1996. 

Wanka, G Hoffman, H Ulbricht, W, Phase Diagrams and Aggregation Behavior of Poly (oxyethylene)-Poly(oxypropylene)-Poly(exyethylene) Triblock copolymers in Aqueous Solutions, Macromolecules 27, 4145, 1994. 

Polyglycols, especially poly(propylene-l,2- or -1,3-glycol). Poly(oxyethylene) and poly(oxypropylene) block copolymers have relatively poor foam control [536]. 

Figure 8. Part of a tetrafunctional network formed from an RA t and RBi polymerization corresponding to Mc°, the molar mass between junction points of the perfect network (a). Detail of the chain structure defining Mc° for HDl reacting with an OPPE, n is the number-average degree of polymerization of each arm with respect to oxypropylene units, (b). Part of the chain structure defining v, the number of bonds in the chain forming the smallest ring structure (C), for the reaction system in (b) (29). Reproduced, with permission, from Ref. 21. Copyright 1980, Stein-...

Figure 5.10 Dependence of the gel fraction, wg, on molar ratio of [OH]/[NCO] groups, ah, for poly(oxypropylene)triol (Niax LG 56)4,4 -diisocyanatodiphenyl-methane system. The dependence has been reconstructed from data of ref. [78]...

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