PPO

Mortensen K 1996 Structural studies of PEO-PPO-PEO triblock copolymers, their micellar aggregates and mesophases a small-angle neutron scattering study J. Phys. Condens Matters A103-A104... 

Acetalresins). Polyoxypiopylene (PPO) (2) and poly (methyl vinyl ethei) (PMVE) (3) have... 

PPO poly(phenyl oxide) SCF self-consistent field ... 

Poly(propylene oxide) [25322-69-4] may be abbreviated PPO and copolymers of PO and ethylene oxide (EO) are referred to as EOPO. Diol poly(propylene oxide) is commonly referred to by the common name poly(propylene glycol) (PPG). Propylene oxide [75-56-9] and poly(propylene oxide) and its copolymers, with ethylene oxide, have by far the largest volume and importance in the polyurethane (PUR) and surfactant industry compared to all other polyepoxides. Articles reviewing propylene oxide (1), poly(propylene oxide) (2—4), other poly(aIkylene oxides) (4), and polyurethanes (5—7) are cited to lead the interested reader to additional detail not in the scope of this article. 

Homopolymers of PO and other epoxides are named a number of ways after the monomer, eg, poly(propylene oxide) (PPO) or polymethjioxirane from a stmctural point of view, polyoxypropylene or poly(propylene glycol) or from the Chemicaly hstracts (CA) name, poly[oxy(methyl-l,2-ethanediyl)], a-hydro- CO-hydroxy-. Common names are used extensively in the Hterature and in this article. 

MggAl2(OH) gC03 -4 H2O, is used to polymerize PO and is activated by calcining at 450°C, a quantitative yield of PPO is obtained at 50°C in 2 hours (96). At Olin, POLY-L polyols have been produced with reduced unsaturation, but the catalyst used to produce them has not been disclosed (97). The use of zinc hexacyanocolbaltate to prepare low unsaturation polyols has been reported (98). 

Table 3. Charges for a 3000 Molecular Weight Glycerol-Initiated PPO Triol...

The unsaturation present at the end of the polyether chain acts as a chain terminator ia the polyurethane reaction and reduces some of the desired physical properties. Much work has been done ia iadustry to reduce unsaturation while continuing to use the same reactors and hoi ding down the cost. In a study (102) usiag 18-crown-6 ether with potassium hydroxide to polymerise PO, a rate enhancement of approximately 10 was found at 110°C and slightly higher at lower temperature. The activation energy for this process was found to be 65 kj/mol (mol ratio, r = 1.5 crown ether/KOH) compared to 78 kj/mol for the KOH-catalysed polymerisation of PO. It was also feasible to prepare a PPO with 10, 000 having narrow distribution at 40°C with added crown ether (r = 1.5) (103). The polymerisation rate under these conditions is about the same as that without crown ether at 80°C. 

A hst of polyol producers is shown in Table 6. Each producer has a varied line of PPO and EOPO copolymers for polyurethane use. Polyols are usually produced in a semibatch mode in stainless steel autoclaves using basic catalysis. Autoclaves in use range from one gallon (3.785 L) size in research faciUties to 20,000 gallon (75.7 m ) commercial vessels. In semibatch operation, starter and catalyst are charged to the reactor and the water formed is removed under vacuum. Sometimes an intermediate is made and stored because a 30—100 dilution of starter with PO would require an extraordinary reactor to provide adequate stirring. PO and/or EO are added continuously until the desired OH No. is reached the reaction is stopped and the catalyst is removed. A uniform addition rate and temperature profile is required to keep unsaturation the same from batch to batch. The KOH catalyst can be removed by absorbent treatment (140), extraction into water (141), neutralization and/or crystallization of the salt (142—147), and ion exchange (148—150). 

Nmr Studies. >H- and C-nmi has been valuable in elucidating the stmctuie of PPO and copolymers of EO and PO, especially since high field nmr has become widely available. 

C-nmr was used to analy2e the stereoregularity of PPO prepared with the diphenyl2inc—water system at various (H2O / ratios (160). 

The composition of PPG—PEG blends has been determined using gpc with coupled density and RI detectors. PEG and PPG have different response factors for the density and RI detectors which were exploited (173). An hplc system with CHROMPAC RP-18C2g column at 298°C and acetonitrile—water or methanol—water as the mobile phase has been used to gather information about the functionaUty of PPO (174). 

Solubility. PPO polyols with a molecular weight below 700 are water soluble. The triol is slightly more water soluble than the diol. The solubihty in water decreases with increasing temperature. This inverse solubiUty causes a cloud point which is important in characteri2ing copolymers of propylene oxide and ethylene oxide. 

Mass Spectrometry. Field desorption mass spectrometry has been used to analy2e PPO (179). Average molecular weight parameters (M and could be determined using either protonated (MH + ) or cation attachment (MNa + ) ions. Good agreement was found between fdms and data supphed by the manufacturer, usually less than 5% difference in all cases up to about 3000 amu. Laser desorption Fourier transform mass spectrometry was used to measure PPG ion and it was claimed that ions up to m/2 9700 (PEG) can be analy2ed by this method (180). 

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