Polymer blends may be made by a variety of ways. A flexible but expensive off-line process of making polymer blends uses solid polymers as starting materials, typically outside the polymerization process that produced the polymer blend components. The polymer blend components are typically first melted or dissolved in a solvent and then blended. These processes are known as melt-blending and off-line solution blending, respectively. In melt blending, the solid, often pelletized or baled, polymer blend components are first melted and then blended together in their molten state. One of the difficulties presented by melt blending is the high viscosity of molten polymers, which makes blending of two or more polymers difficult and often imperfect on the molecular level. In solution off-line blending, the solid, often pelletized or baled, polymer blend components are first dissolved in a suitable solvent to form a polymer solution, and then two or more polymer solutions are blended together. After blending, solution blending requires the extraction of solvent from the blend and drying of the blended polymer. Solution blending can overcome the viscosity issue associated with melt blending, but is expensive due to the need for redissolving the polymer blend components and due to the cost of solvent handling.
The common feature of both melt blending and off-line solution blending is that the polymer blending components are made in separate plants and the solid polymers then are reprocessed either in a molten or in a dissolved state to prepare the final polymer blend. In fact, these off-line blending processes are often operated by so-called compounders, generally independent of the manufacturers of the polymer blend components. These processes add considerable cost to the cost of the final polymer blend. The production and full polymer recovery in separate plants and subsequent reprocessing increases the costs of producing such blends because of the need for duplicate polymer recovery lines and because of the need for separate blending facilities and the energy associated with their operations. Off-line solution blending also requires extra solvent, and facilities for polymer dissolution and solvent recovery-recycle. Substantial reprocessing costs could be saved if the polymer blends could be made in one integrated polymerization plant in-line, i.e. before the recovery and pelletizing of the solid polymer blend components.
The disadvantage of a separate polyolefin blending plant associated with the melt blending and off-line solution blending processes is alleviated with the prior art method of in-line solution blending of polymers using a series reactor configuration. Utilizing the series reactor configuration, product blending may be accomplished in the solution polymerization reactor itself when the effluent of the first solution polymerization reactor is fed into the second reactor operating at different conditions with optionally different catalyst and monomer feed composition. Referring to the two-stage series reactor configuration of FIG. 1 (prior art), the two different polymers made in the first and second reactor stages are blended in the second stage yielding a blended polymer product leaving the second reactor. Such reactor series configuration may be further expanded into more than a two-stage series configuration (three or more reactors in series). Generally, a series of n reactors may produce a blend with as many as n components or even more present in the effluent of the last reactor. Note that in principle, more than n components may be produced and blended in n reactors by, for example, using more than one catalyst or by utilizing multiple zones operating at different conditions in one or more reactors of the series reactor cascade. While mixing in the downstream reactor(s) provides good product mixing, particularly when the reactors are equipped with mixing devices, e.g., mechanical stirrers, such series reactor configuration and operation presents a number of practical process and product quality control problems due to the close coupling of the reactors in the cascade. One of the most important difficulties in commercial practice is ensuring proper blend and monomer ratios to deliver consistent blend quality. Additional complications arise when the blend components have different monomer compositions, particularly when they have different monomer pools, such as in the case of blending different copolymers or in the case of blending homo- and copolymers. Since the monomer streams are blended, there is no option for their separate recovery and recycle mandating costly monomer separations in the monomer recycle lines.
The above-outlined issues with series reactor operations are apparent to those skilled in the art of chemical engineering. These difficulties are particularly significant in polymerization because unlike in small-molecule syntheses, reactor conditions determine not only reactor productivities related to product blend ratio, but also product properties related to controlling the quality of the polymer blend components. For example, FIGS. 2 and 3 show how reactor temperature and pressure affect polymer properties of fundamental importance, such as molecular weight (MW) and melting behavior. Surprisingly, we found that monomer conversion in the reactor also influences these critical product attributes (see FIG. 4). Since in a series reactor cascade the effluent of an upstream reactor flows into the next downstream member of the reactor cascade, the residence time, catalyst concentration, and monomer composition and thus monomer conversion in the downstream reactor cannot be adjusted independently of the operating conditions (particularly of the flow rate) of the upstream reactor. Because of this close and inherent coupling of operating regimes in the reactors of the series cascade, the correlations depicted in FIGS. 2, 3, and 4 further reduce the controllability, flexibility, and thus the usefulness of the in-line blending method in a series-reactor configuration. Ultimately, this greatly reduces the number of blend products that can be made in such a series reactor cascade and makes the blend quality difficult to control.
Applying parallel reactors can overcome the disadvantages related to the direct coupling of the polymerization reactors in an in-line polymer blending applying series reactors. While production flexibility is increased, a parallel reactor arrangement necessitates the installation of blending vessels increasing the cost of the process.
A need thus exists for an improved and cost-effective method of in-line blending of polymers to avoid the issues associated with the prior-art methods, such as melt blending off-line solution blending, and in-line solution blending in a series reactor configuration. More particularly, a need exists for an improved in-line method of blending polymers, especially for an improved in-line method of blending polyolefins, where the residence time, monomer composition, catalyst choice, and catalyst concentration can be independently controlled in each polymer reactor prior to the blending step. There is also a need for a simplified and cost-effective polymer blending process to reduce the number of process steps and the associated investment and operating costs in an integrated polymer production and blending process employing parallel reactor trains for producing the polymer blend components in-line, i.e. without recovering said blend components in their solid state.
USPTO Backgrounds
USPTO Backgrounds