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Reaction Injection Molding

CHE 1754: Principles of Polymer Engineering

Blake Fenton Tim Risch Devon Walker

Process Description Reaction injection molding (RIM) is a process designed to produce intricate polymer molds from the mixing of polymeric reagents [7]. Though the products of RIM can be made very intricate and precise, the process is not overly complicated or difficult. The products of reaction injection molding are factors of the ingredients used, the equipment used, and the process parameters maintained, such as pressure and viscosity. The ingredients used in RIM are the most important part of determining the physical characteristics of the product mold. The principle ingredients for RIM consist of a polyol for polymer chain extension, an isocyanate for the desired type of product, and one or more additives which give the product unique properties. [7]

Figure 1: Example Polyol Figure 1 above shows an example of a polyol used in RIM. Polyols are two or three hydroxyl groups attached along a carbon chain and act as chain extending reagents in RIM. The hydroxyl groups will attack the isocyanates, which in turn are attacked by more polyols [1]. Since there are multiple hydroxyl groups along each chain, each polyol will attack two to three different molecules, thus extending the chain and crosslinking the polymer between multiple chains [1]. Polyols each present a unique structure for the polymers they create [7]. This, combined with the fact that polyols are generally unreactive with one another, leads to the idea of mixing different polyols to blend some of their structural properties in the resulting polymer after RIM [7].

Figure 2: Isocyanate Functional Group Molecules are considered, for this purpose, isocyanates if they contain an isocyanate functional group. Isocyanates are compounds that contain a carbon chain attached to a nitrogen double-bonded to a carbon double-bonded to an oxygen [7]. The double bond between the carbon and the nitrogen typically is broken by the polyols so that another oxygen atom may attach to the carbon and thus increase the chain length. Since a molecule can have multiple isocyanate functional groups, polymerization and crosslinking can occur.

Figure 3: Polyurethane Synthesis Figure 3 shows the polyurethane chemical reaction, often used in the RIM process. In this reaction, urethane acts as the isocyanate and ehtylene glycol acts as the polyol. The hydroxyl group of ethylene glycol attacks an isocyanate group of urethane, causing carbon to become negatively charged, which breaks the double bond with nitrogen. From here, nitrogen becomes negatively charged and takes the hydrogen from the attacking hydroxyl group. Another important reaction in RIM is that of nylon and can be found in Appendix A.

Figure 4: RIM Process Diagram [2]

The mechanical process of reaction injection molding is simpler than the chemistry behind it, and a process diagram is shown in Figure 4. Two tanks, one filled with liquid isocyanate and one filled with a polyol slurry containing the additives are pumped into a mixing chamber [7]. Impingement mixing occurs here, which means the mixing of the two compounds in order to initiate polymerization [1]. Impingement mixing is done at extremely high pressures, typically around 2500 psi [7]. To maintain the desired temperature of the system, the feed to the impingement mixer is constantly being recycled back into the corresponding tank. From the mixing chamber the mixed product is injected into the desired mold and begins the polymerization process. Polymerization will occur immediately upon being mixed and the mold must be filled quickly. After polymerization is sufficient and the product has cooled, the product is removed. Removal is often done before the product has fully cured to increase industrial efficiency, and is post-cured outside of the mold [2]. Nylons, however, are always completely reacted in the mold [2]. Impingement mixing does not involve heating or cooling, so long as the viscosities of the reagents are low. Temperatures to achieve such viscosities are controlled in the tanks or along the process line to the mixer. The time it takes a mixture to polymerize completely is known as the curing time [10]. The cure time for a RIM mold is very fast and typically lies between three and five minutes [3]. The reaction itself is exothermic and the mold will heat as it cures and polymerizes further [3]. Polymerization typically causes the product to expand, creating an internal pressure and filling the mold. Many molds have vents so that expanding polymers have room to expand after the mold has filled and the pressure in the mold is not overly high. Polymer that has been extruded through a vent is simply removed during a finishing process. Since it fills the mold completely, RIM is useful for obtaining very precise and complex mold geometries if desired. Typical Products and Constraints Typical products of RIM include a wide variety of car parts, computer cases, and general electronic plastic containers. Availability of polyurethane reagents and the ability to shape the plastic into any configuration of mold is a feature of RIM [7]. The products can also be made to meet physical demands, such as a car bumper, while still being relatively inexpensive for mass production. The Armstrong Mold Corporation, one of the leading producers of RIM products, gives a listing of the basic properties that their typical polymer products produced by the RIM process and can be found in Appendix B. The size constraint of process used by this company is a mold of up to 48 square inches. The size constraint in RIM is delimited by the time it takes to get the final mixture into the mold. Since the cure times of the mixtures are so fast and the mold should be filled in around ten seconds to avoid polymerization within the mixer, size is determined by the speed of injection after impingement mixing [3]. Temperature control cannot adequately negate the speed of polymerization [2]. The company also has a weight constraint of up to 18 pounds, but again this is a function of the company's inability to produce larger molds. The last metric constraint of this company is a required thickness of no less than 1/4 inches. This is again just a manufacturing concern, since the mold would determine the final thickness of the product. The issue here is the structural integrity of the product during removal from the mold and during transport. RIM will completely fill molds, and thickness would not be a concern otherwise. [13]

Other parameters of their products that the Armstrong Mold Corporation lists are size tolerance, hole size, and draft. The company lists increasing tolerances between plus/minus 0.010 and 0.040 inches for products that range between the sizes of 0 and 48 inches. The tolerance is a factor of the quality of the process the company is using and can be increased or decreased along with the type of process used. The hole size is a non-issue for this company in their molds and this goes back to the RIM process being able to fill the entire mold to its specification. The draft is the angle around edges of a mold, which allow for the removal of the product from the mold to be easier. The company recommends an angle between 1 and 2 degrees, though no angle can also be specified. This is again not an issue of RIM, since it fills molds completely, and is only an issue of mold removal. [13] Polymers and their Characteristics

Figure 5: Nylon 6 Polymers that are processed by RIM include: polyurethane, nylon 6, dicyclopentadiene, polyester, acrylamates, phenolics, and epoxys [17]. Figure 3 shows the molecular structure of polyurethane and Figure 5 shows the molecular structure of Nylon 6. These are two of the most common products of the RIM process. There are two categories that commonly encompass RIM materials. The first include solid polymers. These are processed without blowing agents in order to form flexible and rigid plastics. Solid polymers exhibit thermoplastic-like properties and are commonly used in automotive and agricultural industry. The second category involves foamed polymers. These involve blowing agents to form a capsule of a high-density rugged skin and a lower density core [13]. Common characteristics of the products typically show high heat resistance, thermal insulation, and high dimensional stability [16]. These properties are formed from chemical bonds between adjacent polymer molecules, also known as crosslinking. When exposed to extremely high heat, the polymer chains tend to degrade rather than soften, allowing for potential recycling techniques. The dynamic properties include high strength, low weight, and high impact resistance [4]. RIM polymers, due to the immense crosslinking, offer high resistances to organic and inorganic acids along with low solubility with many solvents [16]. History Reaction Injection Molding was developed in the 1960s by Bayer [11]. It had its first big appearance in the automotive industry when they began to worry about costs for producing

casting equipment. With the low cost of RIM equipment, it was possible to easily produce gaskets and radial seal air filters. Since the main material polyurethane is synthetic, it was easily obtained at a much lower cost than acquiring natural metals and molding them [11]. The toughness and versatility of the RIM products, along with the variety of shapes and sizes that could be created, made it an invaluable resource for companies. Today RIM is used to create a multitude of products including: simulating wood furnishings, water filtration panels, specialty car parts, bowling balls, sports helmets, window frames, domestic refrigerators, and mannequins [4] . Production Rates and Costs Reaction injection molding is mostly used in the mass production of a particular product for an industrial company. Typically, a company can have anywhere from a few hundred to thousands of a particular part produced every year. Depending on the part, production can reach over a million units per year [1]. The part size can be as light as a few ounces, or over thirty pounds [9]. The main advantage of RIM is its cost compared to traditional injection molding. High heat and pressure is needed to melt the thermoplastics used in injection molding. The reaction involved in RIM means less heat and pressure is needed. This lessens the energy cost, as well as the cost for molding materials because the materials do not have to withstand such high temperatures. [6] More recently, processors have adapted the RIM process to compensate for the greater challenge of casting nylon-based monomers and began processing caprolactam-based materials. This innovation leads to a far more cost-effective process for manufacturing parts than machining from a stock shape [9]. Nylon 6 is now one of the more commonly used polymers in RIM. It's very similar counterpart, Nylon 6,6, is used in standard injection molding. However, the melting point of Nylon 6,6 is very high, meaning thermally stable molds must be used and high heating costs exist. The reaction of caprolactam to produce Nylon 6 in RIM rapidly occurs at temperatures much lower than the 265 oC melting temperature of Nylon 6,6. Usually RIM of Nylon 6 is performed between 100 and 160 oC. Although Nylon 6 is not as strong or stiff as Nylon 6,6, it is lighter and cheaper to produce, and still strong enough for most applications [17]. Companies Using RIM Because reaction injection molding is a very cost-effective form of molding, many companies now use the process. No one company dominates the industry because there are so many options. This is partly due to the demand for the production of custom molded parts. Some notable companies in the RIM business are THIEME Corporation, Exothermic Molding Inc., Armstrong Mold Corporation, and Bayer Corporation [5]. Because of the many companies available, the specifications each offers are similar in order to remain competitive in the industry.

Appendix A: Nylon Synthesis

One type of material produced using the reaction injection molding process is Nylon 6. Caprolactam is the monomer Nylon 6 is derived from. The structure of caprolactam, and the polymer chain resulting from its polymerization are shown in below.

Figure 6: Caprolactam and Nylon 6 [8] The key to the process is opening the caprolactam ring. This is usually accomplished through a hydrolysis reaction at the central carbon of the amide functional group.

Figure 7: Opening Caprolactam Ring [8] However, in RIM, a metal catalyst, such as magnesium bromine caprolactam or sodium caprolactam, is used [8]. Below is an example of the caprolactam anion attached to a sodium cation.

Figure 8: Metal Catalyst and Caprolactam [15] In order to initiate the reaction, an initiator is needed. Like most RIM reactions, the initiator is an isocyanate, and in this case, 1,6 hexane diisocyanate is used [17]. The anionic propagation process proceeds by opening the ring at the same central carbon as the hydrolysis reaction. Ring opening connects the monomers and polymerizes the caprolactam into Nylon 6. The reaction ends when the anion is exhausted, or an additive attaches to the end of the polymer chain and terminates the process.

Appendix B: Armstrong RIM Specifications [13]

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