Propylene continuous polymerization

Continuous Simulation, C0NGAS. There are no published data available on propylene continuous polymerization suitable to check the accuracy of the C0NGAS model. However, there is an equation for yield vs. time published by Wisseroth (3 ) for a completely backmixed continuous reactor ... 

As an example of the use of MIXCO.TRIAD, an analysis of comonomer triad distribution of several ethylene-propylene copolymer samples will be delineated. The theoretical triad Intensities corresponding to the 2-state B/B and 3-state B/B/B mixture models are given In Table VI. Abls, et al (19) had earlier published the HMR triad data on ethylene-propylene samples made through continuous polymerization with heterogeneous titanium catalysts. The data can be readily fitted to the two-state B/B model. The results for samples 2 and 5 are shown In Table VII. The mean deviation (R) between the observed and the calculated Intensities Is less than 1% absolute, and certainly less than the experimental error In the HMR Intensity determination. 

MPC [Mitsui Petrochemical] A continuous process for polymerizing propylene, based on the Ziegler-Natta process, but using a much more active catalyst so that de-ashing (catalyst removal) is not required. The catalyst contains magnesium in addition to titanium successive versions of it have been known as HY-HS (high yield, high stereospecifity), HY-HS II, and T-catalyst. Developed jointly by Mitsui Petrochemical Industries, Japan, and Montedison SpA, Italy, in 1975, and now licensed in 56 plants worldwide. 

The compositions of EPDM elastomers are controlled by using the appropriate monomer feed ratio (see Eq. (2.38)) to obtain the desired composition in a continuous polymerization process. In general the excess propylene required is recycled. The molecular weights of EPDM polymers are controlled primarily by chain transfer reactions with added molecular hydrogen (Eqs. (2.86) and (2.87)), as is common with other Ziegler-Natta polymerizations (Boor, 1979). 

To forecast the behavior of a catalyst system in an industrial continuous polymerization, these characteristics should be determined within a wide range of conditions eg, temperature, concentration, and ratios of the various components (activator, external donor, solid catalyst, etc). A laboratory batch-scale test can provide most of this information. A small, simple reactor suitable for these studies is shown in Figure 8. The polymerization can be carried out in a hydrocarbon or liquid propylene. In some cases the pol5unerization test can be performed in the gas phase, provided the reactor is prepared with a suitable heat transfer and catalyst dispersing bed (eg, a salt bed). 

Transition-Metal Alkji and Related Catalysts There continues to be a lively interest in the use of transition-metal alkyl compounds as polymerization catalysts both in the absence and in the presence of alkylaluminium cocatalysts. Hie more active catalysts of this type are invariably supported sterns and indeed it is of some interest that many non-supported transition metal alkyls do not polymerize propylene at all. Sinc this field has been extensively reviewed in recent years by Ballard and also features in an article by Yermakov only the most recent publications will be mentioned in this Report. 

UNIPOL process A process used for polymerizing ethylene to polyethylene and also for polymerizing propylene to polypropylene. Unlike the Ziegler-Natta process, it uses a gas phase process at low pressure. The catalyst is continuously added to the process and the granular product withdrawn. A co-monomer is also usually used in the process. 

Propylene oxide [75-56-9] (methyloxirane, 1,2-epoxypropane) is a significant organic chemical used primarily as a reaction intermediate for production of polyether polyols, propylene glycol, alkanolamines (qv), glycol ethers, and many other useful products (see Glycols). Propylene oxide was first prepared in 1861 by Oser and first polymerized by Levene and Walti in 1927 (1). Propylene oxide is manufactured by two basic processes the traditional chlorohydrin process (see Chlorohydrins) and the hydroperoxide process, where either / fZ-butanol (see Butyl alcohols) or styrene (qv) is a co-product. Research continues in an effort to develop a direct oxidation process to be used commercially. 

The kinetic models for the gas phase polymerization of propylene in semibatch and continuous backmix reactors are based on the respective proven models for hexane slurry polymerization ( ). They are also very similar to the models for bulk polymerization. The primary difference between them lies in the substitution of the appropriate gas phase correlations and parameters for those pertaining to the liquid phase. 

AT is intended to include any and all of the effects of the sorption rate of monomer on the surface, steric arrangement of active species, the addition of the monomer to the live polymer chain, and any desorption needed to permit the chain to continue growing. We assume a steady state in which every mole of propylene that polymerizes is replaced by another mole entering the shell from the gas, so that all of the fluxes are equal to Ny gmol propylene reacted per second per liter of total reactor volume. The following set of equations relates the molar flux to each of the concentration driving forces. 

Figure 6. Simulation of a continuous backmix reactor (propylene gas phase polymerization—kg° = 0,0249 cm/sec, X = 9.68 hr, 400 psia reactor gas composition—99% CsH6,1% inerts)...

UNIPOL [Union Carbide Polymerization] A process for polymerizing ethylene to polyethylene, and propylene to polypropylene. It is a low-pressure, gas-phase, fluidized-bed process, in contrast to the Ziegler-Natta process, which is conducted in the liquid phase. The catalyst powder is continuously added to the bed and the granular product is continuously withdrawn. A co-monomer such as 1-butene is normally used. The polyethylene process was developed by F. J. Karol and his colleagues at Union Carbide Corporation the polypropylene process was developed jointly with the Shell Chemical Company. The development of the ethylene process started in the mid 1960s, the propylene process was first commercialized in 1983. It is currently used under license by 75 producers in 26 countries, in a total of 96 reactors with a combined capacity of over 12 million tonnes/y. It is now available through Univation, the joint licensing subsidiary of Union Carbide and Exxon Chemical. A supported metallocene catalyst is used today. 

Experimental Apparatus and Operating Conditions. The polymerization of propylene in the presence of a heterogeneous catalyst and a solvent occurred at a relatively low partial olefin pressure and was carried out in an apparatus continuously fed during the reaction with the olefin in the gaseous state at constant pressure (Fig. 14). 

Tracer studies have been used in an attempt to determine the nature of the ends of the chain but these were as unsatisfactory as for propylene. Feldman and Perry (83) used triterated methanol to react the polyethylene from a titanium tetrachloridetrialkylaluminum catalyst. They found a continual increase in the number of polymeric chain ends which react with the tritium. This agrees with the results of Roha and Beears (84) who showed the very rapid exchange of alkyls which took place when ethylene was grown on a Ziegler catalyst in the presence of excess alkylaluminum chloride. In these experiments only an extremely small... 

Preparation of Poly (propylene ether) Polyols. The polymerization of propylene oxide with zinc hexacyanocobaltate complexes in the presence of proton donors results in the production of low-molecular-weight polymers. Table V shows the variety of types of compounds that have been found to act this way. Since these compounds end up in the polymer chains, it seems reasonable to call them chain initiators. Thus, in essence, each of these compounds is activated by the catalyst to react with propylene oxide to form a hydroxylpropyl derivative. Thereafter, the reaction continues on the same basis, with the proton of the hydroxyl group reacting with further propylene oxide. This sequence is shown here with 1,5-pentanediol as the initiator. The hydroxyl... 

Figure 8 shows the characterization of these poly (propylene ether) diols by gel-permeation chromatography. There is a shift in the peak position to lower elution volumes, in accord with an increase in molecular weight with each monomer increment polymerized. The molecular-weight distributions of the three diols are similar and remain narrow after the addition of monomer increments. Since all of the molecules apparently continued to grow, this polymerization must proceed with very little chain termination under these conditions. 

Indeed, free radical polymerization of fluoroolefins continues to be the only method which will produce high-molecular weight fluoropolymers. High molecular weight homopolymers of TFE, CFC1 = CF2, CH2CF2, and CH2=CHF are prepared by current commercial processes, but homopolymers of hexafluoro-propylene or longer-chain fluoroolefins require extreme conditions and such polymerizations are not practiced commercially. Copolymerization of fluoroolefins has also led to a wide variety of useful fluoropolymers. Further discussion of the subject of fluoroolefin polymerization may be found elsewhere and is beyond the scope of this review [213-215]. 

A common example of a copolymer is an ethylene-propylene copolymer. Although both monomers would result in semi-crystalline polymers when polymerized individually, the melting temperature disappears in the randomly distributed copolymer with ratios between 35/65 and 65/35, resulting in an elastomeric material, as shown in Fig. 1.19. In fact, EPDM rubbers are continuously gaining acceptance in industry because of their resistance to weathering. On the other hand, the ethylene-propylene block copolymer maintains a melting temperature for all ethylene/propylene ratios, as shown in Fig. 1.20. 

In polymerization at low temperatures, the time required to form one polymer chain is long enough to consume one monomer fully and allow the subsequent addition of another one. Thus, it becomes possible to synthesize block copolymers, provided that the polymerization (especially when it is catalyzed by hafnocenes) starts with propylene and, after the propylene is nearly consumed, continues with ethylene. 

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