Copolymer of propylene oxide and allyl

Abbreviation for copolymer of propylene oxide and allyl glycidyl ether. 

The only commercially available material in this class, Parel, is a copolymer of propylene oxide and allyl glycidyl ether. 

The mechanical properties of propylene oxide rubbers (copolymers of propylene oxide and allyl glycidal ether) depend both on the catalyst used in preparing the polymer and on the comonomer content. The mechanical properties are very much influenced by the ability of propylene oxide stereosequences in the copolymer to crystallize. The crystalline material can give a substantial Increase in modulus and in the strength of the polymer on stretching. 

Parel elastomer, a copolymer of propylene oxide and allyl glycidyl ether, has a combination of properties that make it very useful in many rubber applications. It can be vulcanized with a conventional mixture of sulfur and accelerators. The cured elastomer has a low glass transition temperature (approximately -55 to -60 C.), and the excellent dynamic properties of natural rubber. It can be made very stable to high temperature oxidative degradation, and is better than neoprene in this respect, when NBC is added as a stabilizer. 

This elastomer is a sulfur-vulcanizable copolymer of propylene oxide and allyl glycidyl ether. Its vulcanizates are particularly attractive for dynamic uses, where high resihence, excellent flex life, and flexibility at extremely low temperatures are required. It performs similarly to NR in these applications, but it also has the added advantages of (1) good resistance to aging at high temperatures, (2) good ozone resistance, and (3) moderate resistance to loss of properties in contact with fuels and/or some solvents. The surfaces of this elastomer should be... 

The discovery of coordinate polymerization of oxirane led to an enormous expansion in the range of polyether structures that could be synthesized. Some of the remarkable synthesis chemistry is outlined in Section III. Coordinate copolymerization further increased the range of polymer structures that could be synthesized in highly controlled ways. Two examples have already been described copolymers of epichlorohydrin and ethylene oxide (71) and of propylene oxide and allyl glycidyl ether (94, 137). The activation energy for copolymerization of epichlorohydrin and maleic anhydride was found to be 14.5 kcal/mol, and the polymerization rate is dependent on temperature and proportional to catalyst concentration (138-140). 

Another commercial application of organoaluminum compounds is as catalysts for the ring-opening polymerization of epoxides to form homopolymers of epichlorohydrin (ECH) and copolymers and terpolymers of ECH, ethylene oxide, propylene oxide, and allyl glycidyl ether.The resulting... 

The analogous phenomenon was first reported by Bergbreiter etal. [17, 18]. In the presence of phosphorus-bonded block copolymers of ethylene oxide and propylene oxide as ligands ( smart ligands ), rhodium-catalyzed hydrogenation of maleic acid or allyl alcohol in the aqueous phase would show the same anti-Arrhenius reactivity. 

Propylene oxide rubbers (PO rubbers) These materials were first announced in 1963 (Gruber et ai, 1963 1964) and are copolymers of propylene oxide with a cure-site monomer (usually allyl glycidyl ether used to a proportion of about 10% of the total monomer). Their structures may be represented by ... 

These include copolymers of propylene sulphide with 3-10% of allyl glycidyl thioether and which may be considered as a thio-analogue of the propylene oxide-allyl glycidyl ether rubber briefly mentioned in Section 19.5 ... 

Polyether Polyols. Polyether polyols are addition products derived from cyclic ethers (Table 4). The alkylene oxide polymerization is usually initiated by alkali hydroxides, especially potassium hydroxide. In the base-catalyzed polymerization of propylene oxide, some rearrangement occurs to give allyl alcohol. Further reaction of allyl alcohol with propylene oxide produces a monofunctional alcohol. Therefore, polyether polyols derived from propylene oxide are not truly difunctional. By using zinc hexacyano cobaltate as catalyst, a more difunctional polyol is obtained (20). Olin has introduced the difunctional 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-catalyzed homopolymerization of tetrahydrofuran. Copolymers derived from tetrahydrofiiran and ethylene oxide are also produced. 

A number of chlorinated poly(ethers) have practical uses. A common compound from this group is polyepichlorohydrin, [-CH(CH2CI)CH20-]n. Polyepichlorohydrin has practical applications as an elastomer and is used in copolymers with propylene oxide, ethylene oxide, allyl glycidyl ether (1-allyloxy-2,3-epoxypropane), etc. Another example is poly oxy[2,2 -bis(chloromethyl)-1,3-propandiyl] or poly[oxy-1,3-(2,2 -dichloromethyl)propylene], CAS 25323-58-4, which can be used as inert lining material for chemical plant equipment, as adhesive, coating material, etc. This macromolecule can be prepared starting with pentaerythritol in the sequence of reactions shown below ... 

In most cases the catalytically active metal complex moiety is attached to a polymer carrying tertiary phosphine units. Such phosphinated polymers can be prepared from well-known water soluble polymers such as poly(ethyleneimine), poly(acryhc acid) [90,91] or polyethers [92] (see also Chapter 2). The solubility of these catalysts is often pH-dependent [90,91,93] so they can be separated from the reaction mixture by proper manipulation of the pH. Some polymers, such as the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers, have inverse temperature dependent solubihty in water and retain this property after functionahzation with PPh2 and subsequent complexation with rhodium(I). The effect of temperature was demonstrated in the hydrogenation of aqueous allyl alcohol, which proceeded rapidly at 0 °C but stopped completely at 40 °C at which temperature the catalyst precipitated hydrogenation resumed by coohng the solution to 0 °C [92]. Such smart catalysts may have special value in regulating the rate of strongly exothermic catalytic reactions. 

Manufacture. Propylene oxide is copolymerized with allyl glycidyl ether in an aliphatic, aromatic, or chlorinated hydrocarbon solution using Vandenberg-type catalysts. A complete conversion and a uniform copolymer is obtained containing about 6% of AGE. 

The polymerization o oxetanes with cationic catalysts has been studied by many investigators. (1.H2) RoseC. ), in particular, first reported the homopolymerization of the parent compound, tri-methylene oxide (TMO), with a Lewis acid catalyst, boron trifluoride. The use of coordination catalysts to polymerize oxetanes has been reported in the patent literature by Vandenberg.W In this work, Vandenberg polymerized oxetanes with the aluminum trialkyl -water-acetylacetone coordination catalyst (referred to as chelate catalyst) that he discovered for epoxide polymerization . This paper describes the homo- and co-polymerization of TMO with these coordination catalysts. Specific TMO copolymers, particularly with unsaturated epoxides such as allyl glycidyl ether (AGE), are shown to provide the basis for a new family o polyether elastomers. These new elastomers are compared with the related propylene oxide-allyl glycidyl ether (PO-AGE) copolymer elastomers. The historical development and general characteristics of polyether elastomers and, in particular, the propylene oxide elastomers, are reviewed below. 

For polyethers in polysiloxanes, allyl or butyl alcohol (R ) is commonly used as a starting molecule. The most popular monomers for polyethers are ethylene oxide (EO), propylene oxide (PO), and mixtures thereof. The effect of their ratio can be described with the hydrophilic-lipophilic balance (FILB) concept, which will be discussed later [11]. The higher the PO content, the more hydrophobic is the corresponding polyether. Thus, by varying the composition of the polyethers, sometimes denoted as polyoxyalkylene, it is possible to adjust the polarity of the polydimethylsiloxane polyether copolymer. A macroscopic measure for the polarity of both polyethers and polyethersi-loxanes is the cloud point of a 1% aq. solution. The higher it is, the more hydrophilic is the molecule. In this chapter we will denote these compounds as polyethersiloxanes. It is possible to design silicone surfactants that are suitable for aqueous and nonaqueous systems. 

TMO with these coordination catalysts. Specific TMO copolymers, particularly with unsaturated epoxides such as allyl glycidyl ether (AGEJ, are shown to provide the basis for a new family of polyether elastomers. These new elastomers are compared with the related propylene oxide-allyl glycidyl ether (PO-AGE) copolymer elastomers. The historical development and general characteristics o polyether elastomers and, in particular, the propylene oxide elastomers, are reviewed below. 

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