Alkoxylation Propylene oxide

Scientific Design Company, Inc. Alkoxylates Propylene oxide/ethylene oxide and various chain starters Unique reactor - catalyzed liquid phase is finely dispersed into a PO/EO vapor stream 80 2001... 

Hydrogen Sulfide andMercaptans. Hydrogen sulfide and propylene oxide react to produce l-mercapto-2-propanol and bis(2-hydroxypropyl) sulfide (69,70). Reaction of the epoxide with mercaptans yields 1-aLkylthio- or l-arylthio-2-propanol when basic catalysis is used (71). Acid catalysts produce a mixture of primary and secondary hydroxy products, but ia low yield (72). Suitable catalysts iaclude sodium hydroxide, sodium salts of the mercaptan, tetraaLkylammonium hydroxide, acidic 2eohtes, and sodium salts of an alkoxylated alcohol or mercaptan (26,69,70,73,74). 

Propylene oxide has found use in the preparation of polyether polyols from recycled poly(ethylene terephthalate) (264), haUde removal from amine salts via halohydrin formation (265), preparation of flame retardants (266), alkoxylation of amines (267,268), modification of catalysts (269), and preparation of cellulose ethers (270,271). 

Alkoxylation Ethylene and/or propylene oxides Alkoxylated castor oils... 

Phosphoric acid esters based on alkylene oxide adducts are of great interest. Their properties can be altered by the length and structure of the hydrophobic alkyl chain. But they are also controlled by the kind and length of the hydrophilic alkyleneoxide chain. The latter can easily be tailored by selection between ethylene oxide and propylene oxide and by the degree of alkoxylation. 

If primary alcohols with a straight chain of 10-20 carbon atoms are initially alkoxylated by a mixture of ethylene and propylene oxides followed by phosphorylation, a pour point depression to 8°C will occur, whereas phosphate esters derived from nonylphenol are liquid at temperatures as low as 2°C. Phosphoric acid esters on the base of linear primary alcohols (Cn-Cl5) generally solidify below 24°C [50] (Table 2). 

Alkoxylated polyethyleneimines are obtained by reacting polyethylene-imine with a molecular weight of 2500 to 35,000 with an excess of propylene oxide and ethylene oxide with respect to the ethyleneimine unit in the... 

In general, polyalkylene polyamides-amines are obtained by the condensation of polyalkylenepolyamines with dicarboxylic acids. The materials are alkoxylated with an excess of ethylene oxide or propylene oxide or 1,2-butylene oxide [149],... 

The only large-scale application of sucrose ethers appears to be to use poly-(9-(hydroxylpropyl) ethers, generated by alkoxylation with propylene oxide, as the polyol component for rigid polyurethanes —sucrose itself gives only brittle ones—which are used primarily in cushioning applications. The structures of these products, that is, the positions at which sucrose is alkoxylated and then carbamoylated with diisocyanates, and the type(s) of cross-linking involved, are not well defined though. 

As a general rule, the addition of ethylene oxide to a resin backbone will tend to increase the water solubility of the compound. The addition of propylene oxide or butylene oxide to the resin will tend to increase the hydrocarbon solubility of the compound. Often, the dehazer or demulsifier can be made to perform selectively in oil-water systems by adding both ethylene oxide and propylene oxide to the same molecule. Performance and solubility of the alkoxylated compound can then be finely tuned by closely controlling the amount and order of epoxide addition. A random EO-PO based fuel demulsifier is shown in FIGURE 6-6. 

However, the uncovered silica surface consisting in residual silanols could induce indesirable competitive reaction from propylene oxide treatment such as epoxide opening and alkoxylation of the surface. In order to overcome these drawbacks, the uncovered surface of the Cl-MTS 3 was previously passivate with hexamethyldisilazane treatment before the ligand 1 was anchored according to scheme 3. 

Alkoxylation with, for example, propylene oxide (PO). Preferred amine is triethanolamine, or ammonia and other alkanolamines used amine can also be quaternized Best example is triethanol with 14.9 PO units Contains vinyl ester acetal functionalities besides some unreacted vinyl alcohol monomer units. Preferred aldehyde is butyraldehyde Backbone, for example, polyalkylene glycol, polyalkyl-eneimine, polyether, or polyurethane, and active functional side groups made from grafting VP or VCap to backbone using radical initiators TBA (tributylammonium groups)... 

Last (but not least) propylene oxide undergoes rearrangement in the presence of base and forms allyl alcohol, thus forming in situ initiators during the alkoxylation process. Unless properly accounted for, this decreases the molecular weight of the polyether produced. 

A wide range of products, including every class and type of surfactant, has been found to exhibit demulsification properties. The most commonly used products in lubricant formulations contain anionic surfactants such as alkyl-naphthalene sulphonates. Nonionic alkoxylated alkyl-phenol resins and block copolymers of ethylene oxide and propylene oxide are also used. 

Aminic polyols are low molecular weight adducts of propylene oxide (PO) [and/or ethylene oxide (EO)] made from aliphatic or aromatic polyamines such as ethylenediamine (EDA), diethylene triamine (DETA) [1, 2], ortho-toluene diamine (o-TDA) [3, 4] or diphenylmethanediamine (MDA) [2, 5, 6]. Because these starters are liquid at room temperature (EDA, DETA) or low melting point solids (o-TDA, MDA), they are alkoxylated in the absence of solvents. 

Mannich polyols is a very important group of aromatic polyols obtained by the alkoxylation with propylene oxide (PO) [(and/or ethylene oxide (EO)] of the Mannich bases obtained by classical Mannich reaction between phenols (for example phenol, p-nonylphenol), formaldehyde and alkanolamines (diethanolamine, diisopropanolamine, monoethanolamine, monoisopropanolamine and so on). Synthesis of Mannich polyols is divided into two important steps ... 

In surfactant manufacture, propylene oxide (PO) is employed both as a hydrophobe (see Section 2.3 above), and as a modifier for poly(ethylene oxide). Propylene oxide is similar to EO except that it contains an additional methyl group, which adds steric bulk, and is significantly more hydrophobic in nature. If PO is inserted in the middle of an poly(ethylene oxide) chain, different properties (e.g. greater liquidity) are obtained. Since this approach requires three separate alkoxylations, it is only used when modification of specific properties is required. More common is the use of PO to cap the end of the poly(ethylene oxide) chain. This significantly reduces foaming, which can be critical in certain applications (e.g. machine dishwashing). 

Polymeric amido-amine alkoxylated trietylene tetramine Adducts of aliphatic amines with mono- and diepoxides and ketones (i.e. amine-epoxy adducts) Diethylenetriamine-ethylene oxide adduct Ethylene diamine adduct to solid epoxy Triethylenetetramine-propylene oxide adduct... 

Althongh the ethoxylate structure is shown, alcohol alkoxylates can contain nnits of ethylene oxide, propylene oxide, butylene oxide or mixtnres. Alkyl phenol ethoxylates technically are alcohol ethoxylates however, they are discnssed separately below. 

Rigid PUR foam wastes were simultaneously aminolyzed with NH, ethylene diamine, diethylene triamine, hexamethylenediamine, or ethanolamine and alkoxylated by ethylene oxide, propylene oxide, butylene oxide, phenyl glycidyl ether, or styrene oxide optionally in the presence of a hydroxyl containing tert-amine (dimethyl ethanol... 

The products are prepared by the alkoxylation of cetyl alcohol or stearyl alcohol using ethylene oxide or propylene oxide. In the second step, the intermediate is reacted with acryhc acid, meth-acrylic acid or a mixture from these acids. When the esterification is completed, the unreacted acid is distUled off from the product under high vacuum. An additional purification of the ester is not necessary (28). The reaction is shown in Figure 5.4. 

It was during the 1940s that the base-initiated polymerization of propylene oxide began to be used to produce products that are still in use today (14). In a series of patents by H. R. Rife and F. H. Roberts (15), poly (propylene oxide)s are described that are initiated in the presence of alcohols to produce ether propoxylates. These liquid polymers had methoxy or butoxy groups on one end of the poly ether chain and were used as lubricants and hydraulic fluids. This work was quickly followed by other derivatives, which included esters and mixed alkoxylates of propylene oxide and ethylene oxide (16). Uses included antifoams and emulsifiers, coating solvents, ceramic glazes and binders, and synthetic lubricants for internal combustion engines (17). 

Block copolymers of alkylene oxides were introduced as PLURONIC polyols by Wyandotte, now BASF Wyandotte Corporation, in 1951. The first products were made by alkoxylation of propylene glycol with propylene oxide to a molecular weight of about 900, followed by further reaction with ethylene oxide. These products can be generally characterized by the formula... 

A few examples of polymerization reactions catalyzed by MOFs are reported [161]. Zn carboxylate [162] was shown to catalyze the polymerization of propylene with CO to polycarbonates (M = 75,000g/mol). Alkoxylation of propylene glycol or acrylic acid with ethylene/propylene oxide resulted in polyols. Radical polymerization of divinylbenzene was performed using [M Cbdcj CtedjJ (M=Cu, Zn) [163-165]. 

Alkoxylated perfluoroalkane sulfonamides have been prepared by reacting aliphatic polyamines with less than the stoichiometric amount of a perfluoroalka-nesulfonyl fluoride and alkoxylating the reaction product with ethylene oxide or propylene oxide [233] ... 

For alkoxylates were propylene oxide is used to modify ethoxylates, see - fatty alcohol ethoxylates. 

P. are prepared by - alkoxylation of the starting polyols with ethylene oxide or propylene oxide. The length of the polyether chains is regulated by the amount of alkylene oxide and the reaction time (acidifying). The kind of isocyanate and the structure of the p. command the properties and the uses of the resulting polyurethanes ... 

As mentioned in Chapter 2, alkylphenol alkoxylates can be fused with molten alkali to decompose ethylene oxide and propylene oxide groups, leaving the starting alkylphenol. This is easily characterized by GC or GC-MS, as well as by spectroscopic methods (80,81). 

---