Copolymers tank reactor polymerization

Third-generation high yield supported catalysts are also used in processes in which Hquid monomer is polymerized in continuous stirred tank reactors. The Hypol process (Mitsui Petrochemical), utilizes the same supported catalyst technology as the Spheripol process (133). Rexene has converted the hquid monomer process to the newer high yield catalysts. Shell uses its high yield (SHAC) catalysts to produce homopolymers and random copolymers in the Lippshac process (130). 

Continuous-flow stirred tank reactors are widely used for free-radical polymerizations. They have two main advantages the solvent or monomer can be boiled to remove the heat of polymerization, and fairly narrow molecular weight and copolymer composition distributions can be achieved. Stirred tanks or... 

Figure 1.11 Schematic of BASF s stirred tank emulsion polymerization reactors (dated 1940) for the production of styrenic copolymers (courtesy of BASF, Ludwigs-hafen)...

Low-temperature solution processes are state-of-the-art for the production of ethylene/propylene or ethylene/propylene/diene elastomers (EPDR or EPDM). A continuous stirred-tank reactor (CSTR) or a series of two or even more such reactors is used [2]. n-Hexane, n-heptane, or Ce, C7 fractions are the solvents. Catalyst, co-catalyst and other compounds are introduced with the solvent into the reactor. The monomers (ethylene, propylene) are injected as gases other olefins are introduced in liquid form. The polymerization process runs around 50 °C and at pressures up to 2 MPa. Downstream the catalyst/co-catalyst system is deactivated and their residues are dissolved in dilute acid or aqueous NaOH. The copolymer is stabilized with an antioxidant. Steam treatment removes the rest of the solvent and monomers, and agglomerates the product to crumbs. These crumbs are then dried and finished to bales or pellets. 

PE-LLD and even PE-VLD can further be synthesized with metallocenes and methylalumoxanes in the bulk ethylene (high-pressure) process. The polymerization is performed in a stirred tank reactor at temperatures above 120°C and pressures of at least 50 MPa [65, 66]. The copolymer continuously leaves the reactor with excess ethylene, then the ethylene is vented and recycled into the polymerization reactor. The polymer melt is transferred into pellets. In this case the comonomers are propylene, 1-butene, and 1-hexene. 

In addition to the above investigations, free-radical high-pressure polymerizations should also be studied in continuously operated devices for three reasons. (1) Because of the wealth of kinetic information contained in the polymer properties, product characterization is mandatory. Sufficient quantities of polymer, produced under well defined conditions of temperature, pressure, and monomer conversion, are best provided by continuous polymerization, preferably in a continuously stirred tank reactor (CSTR). (2) Copolymerization of monomers that have rather dissimilar reactivity ratios, such as in ethene-acry-late systems, will yield chemically inhomogeneous material if the reaction is carried out in a batch-type reactor up to moderate conversion. To obtain larger quantities of copolymer of analytical value, the copolymerization has to be performed in a CSTR. (3) Technical polymerizations are exclusively run as continuous processes. Thus, in order to stay sufficiently close to the application and to investigate aspects of technical polymerizations, such as testing initiators and initiation strategies, fundamental research into these processes should, at least in part, be carried out in continuously operated devices. 

Polymerizations. Polymerizations were performed in solution with a 0.5-L continuous stirred tank reactor this apparatus provided polymers of constant composition. After steady-state operation was obtained (approximately three residence times, see Figure 1), 10-mL samples were periodically taken from the effluent, added to 200 xL of a hydroquinone solution, and stored at 10 °C. These samples were subsequently analyzed by HPLC to estimate the mean and variance of the residual monomer concentration and copolymer composition. The polymerization temperatures were 45 and 60 °C for the dimethylamines and 50 °C for DADMAC. The initial monomer concentration was 0.5 mol L" and the monomer feed ratio was varied between 0.3 and 0.7. Azocyanovaleric acid (ACV, Wako Chemical Co.) and potassium persulfate (KPS, BDH Chemicals) were used to initiate the reaction. The solution was agitated at 300 1 rpm for the duration of the polymerization. 

Continuous stirred-tank reactors (CSTRs) are used for large productions of a reduced number of polymer grades. Coordination catalysts are used in the production of LLDPE by solution polymerization (Dowlex, DSM Compact process [29]), of HDPE in slurry (Mitsui CX-process [30]) and of polypropylene in stirred bed gas phase reactors (BP process [22], Novolen process [31]). LDPE and ethylene-vinyl acetate copolymers (EVA) are produced by free-radical polymerization in bulk in a continuous autoclave reactor [30]. A substantial fraction of the SBR used for tires is produced by coagulating the SBR latex produced by emulsion polymerization in a battery of about 10 CSTRs in series [32]. The CSTRs are characterized by a broad residence time distribution, which affects to product properties. For example, latexes with narrow particle size distribution cannot be produced in CSTRs. 

Commercial implementation of emulsion polymerization is mostly carried out in stirred-tank reactors operated semicontinuously. Continuous stirred-tank reactors (CSTRs) are used for the production of some high-tonnage emulsion polymers such as SBR. Batch processes are only used to polymerize monomers with similar reactivities and low heat generation rate (e.g., acrylic-fluorinated copolymers for textile apphcations). 

These linear elastomers are produced by coordination polymerization using a Phillips or Z-N catalyst at low P and T. Here belongs Mxsten XLDPE from Eastman Chem. and Attane ULDPE from Dow. The first metallocene-catalyzed VLDPE was a hexene copolymer with p = 0.912 g mL made in the UNIPOL gas-phase process with Z-N catalyst and introduced by ExxonMobil as Exceed metallocene VLDPE. The resin has outstanding sealing properties (hot tack and seal strength) compared with ZN-VLDPE. The solution polymerization in a hydrocarbon usually is carried out in a continuously stirred tank reactor (CSTR), at r = 160-300 °C and P = 2.5-10 MPa with the residence time of 1-5 min [Dow in 1992 and UCC in... 

In a recent work, formation of block multipolymers from radicalized VDC copolymer particulates has been demonstrated (Caneba et al., 2008). Using the two-stage stirred-tank reactor system (Fig. 4.2.1), recipes and conditions were generated using high-throughput experimentation methods. From cloudpoint experiments (Table 1.1.3), it has already been established that the solvent for the VDC polymerization via FRRPP process is azeotropic MEK/i-butanol. 

Liquid monomer is polymerized in continuous stirred tank reactors in a number of processes. The Hypol process, developed by Mitsui Petrochemical, uses a cascaded series of stirred reactors for homopolymerization, followed by fluidized bed gas-phase reactors for copolymerization (274). El Paso (now Himtsman) converted the Rexall liquid monomer process to use high yield catalysts eliminating the sections required for deashing and removal of atactic material (275). Shell (now Basell) developed the LIPP process to produce homopolymers and random copolymers, using their high yield catalysts. 

Copolymer composition can be calculated as a function of monomer composition when the polymer is formed by free radical polymerization in a CSTR (continuous stirred tank reactor). Consider two monomers 1 and 2 as starting materials for forming a copolymer with repeat units of 1 and 2. The initiation can be effected by thermal means or by using a peroxy initiator. 

As discussed above, it was clear that ethylene/1-butene copolymers possessed significantly improved mechanical properties compared to ethylene homopolymer products, so that a commercial particle-form reactor design was needed that could provide polyethylene copolymers over a range of Flow Index values with sustained operability over extended periods of time without reactor shut down. Adding 1 -butene to the polymerization process made the autoclave stirred tank reactor even more difficult to operate, as reactor wall fouling problems persisted and in some cases polymer particle morphology was reduced due to some polymer components becoming soluble in the n-pentane. 

Poehlein [81] identified major problems encountered with the development of continuous emulsion polymerization processes. It was shown that the development of commercial continuous emulsion polymerization processes involves the consideration of many factors associated with process design and product quality. These factors include the effects of inhibitor, polymerization rate, particle size distribution, copolymer composition, addition strategy of feed streams, unsteady-state operation, and reactor design on continuous emulsion polymerization processes. The author then used a two-continuous stirred tank reactor series to elucidate key continuous emulsion polymerization mechanisms and generate the knowledge necessary for the development of commercial continuous processes. 

Choice of reactor can also have an influence on polymer composition. In batch copolymerizarions, simultaneous polymerization of two or more monomers is often complicated by the different reactivities of the two monomers. This preferential monomer consumption can create a composition drift during chain growth and therefore a tapered copolymer composition. In contrast, a continuous srirred-tank reactor (CSTR) is controlled at steady state, thereby ensuring a homogeneous copolymer composition. 

Fig. 12. Unipol PP process where A is the polymerization reactor B, recycle gas compressor C, recycle gas cooler D, product discharge tank E, impact copolymer reactor F, recycle gas compressor G, recycle gas cooler and H, product discharge tank (134).

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