HIGHLIGHT

Experimental Techniques in High-Vacuum Anionic Polymerization

DAVID UHRIG,1 JIMMY W. MAYS1,2 Chemical Sciences Division and Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831
2

Department of Chemistry, 655 Buehler Hall, University of Tennessee, Knoxville, Tennessee 37996

Received 3 March 2005; accepted 16 July 2005

DOI: 10.1002/pola.21016 Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: Experimental methods used in high-vacuum anionic polymerization are described in detail, with extensive illustrations to demonstrate proper procedures and techniques. These descriptions include construction and operation of the vacuum line, handling purication chemicals, ampulization techniques, short-path distillations, ini-

tiator synthesis, polymerization procedures, and linking reactions using chlorosilanes. A primary emphasis is placed on safety. We believe that this review of these methods will be useful to scientists working in the eld of anionic polymerization and may also benet other researchers in performing tasks requiring ultra-high-purity

reaction conditions.
Chem 43: 61796222, 2005

C V 2005 Wiley

Periodicals, Inc. J Polym Sci Part A: Polym

Keywords: anionic polymerization; break-seal; chlorosilane; glassblowing; high-vacuum line; organolithium reagent

INTRODUCTION
The high-vacuum technique employed in classical anionic polymerization methodology requires highly developed and specialized skills. The polymer scientist must possess both an adept glassblowing ability and a thorough understanding of the behavior of compounds,
Correspondence to: D. Uhrig (E-mail: uhrigdw@ornl.gov)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 61796222 (2005) C V 2005 Wiley Periodicals, Inc.

volatile and nonvolatile, in a vacuum environment. Classic reviews of these techniques that remain relevant today were written by Fetters1 and by Morton and Fetters.2 Hadjichristidis et al.3 published a more recent technical review that very well captures many of the advances made within this synthetic discipline over the last 20 years and contains excellent descriptions of the basic high-vacuum procedures, reagent preparation and purication, polymerization techniques, and some details on the synthesis of complex architectures using anionic polymerization.
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Controlled anionic polymerization is a unique synthetic means toward a large range of model linear and branched polymers and copolymers.47 Very recently, much new and interesting work has been accomplished. Hogen-Esch and coworkers prepared macrocyclic polymers through the strategy of (1) difunctional initiation of a monomer and (2) coupling the resultant macromolecular dinucleophiles with dielectrophiles under conditions of high dilution. Specically, macrocyclic polystyrene (PS) was prepared from either metallo-naphthalide or bis (benzylide) initiation, and the resultant LiPSLi or KPSK dianions were coupled into either methylene bromide or 1,4-bis(bromomethyl)benzene.8 In a similar manner, macrocyclic vinyl aromatic polymers [viz., both poly(2-vinylnaphthalene) and poly(2-vinyl-9,9-dimethyluorene)] were prepared with the same strategy.9 Pitsikalis and coworkers synthesized block copolymers of styrene and either stearyl methacrylate10 or decyl methacrylate.11 Vazaios and coworkers12 prepared triblock copolymers and pentablock terpolymers of nhexyl isocyanate with styrene and/or isoprene. These polymers were prepared through sodium naphthalide initiation, sequential addition of monomers, and addition of sodium tetraphenylborate to prevent unwanted back-biting during polymerization of the isocyanate. Linear tetrablock quaterpolymers of styrene, isoprene, dimethylsiloxane, and 2-vinylpyridine were prepared by Fragouli and coworkers.13 This multiblock copolymer synthesis was accomplished through independent asymmetric sequential polymerizations of the four monomers, the intermediate products of which were sequentially linked into a heterobifunctional linking agent bearing one chlorosilyl functionality and one benzylic chloromethyl functionality. Dumas and coworkers14 prepared star block terpolymers of styrene, tert-butyl methacrylate, and ethylene oxide. This synthesis was accomplished by using an approach based on 1,1-diphenylethylene (DPE); polystyryllithium (PSLi) was end-capped with a siloxy-protected DPE compound, and the resultant heterobifunctional macroinitiator was then used to polymerize ethylene oxide and tert-butyl methacrylate, in turn. In another set of DPE-based synthetic experiments, Higashihara and Hirao15 prepared asymmetric star polymers of three or four different compositional segments. With the compound 1,1-bis(3-chloromethylphenyl)ethylene and a variety of polymerization and linking sequences, star polymers were made from styrene, isoprene, 4-(trimethylsilyl)styrene, and 4-methoxystyrene. Quirk and coworkers exploited anionic polymerization as a means of end functionalization. In one such report, polyisoprenyllithium (PILi) and polybutadienyllithium ( PBLi) were cleanly functionalized with a terminal hydroxy group by end capping with formalde-

hyde.16 In a separate set of experiments, polymeric organolithium compounds were derived to make dienefunctionalized macromonomers; in this synthesis, the macromolecular organolithium species were end-capped with 3,4-epoxy-1-butene, with subsequent dehydration chemistry yielding the macromonomers.17 Contrastingly, as the new chemistry discoveries progress rapidly, the high-vacuum techniques themselves remain, in many instances, nearly timeless. It is therefore worthwhile that we present this article, intended as a companion work to the aforementioned earlier technical reviews, which provides additional and more detailed information on exactly how to conduct essential manipulationsto make such tasks more technically accessible to scientists wishing to successfully accomplish them. The extensive sketches within the text are designed to aid in implementation of the written descriptions. A primary emphasis is placed on safety. In addition to this consideration, the ability to work with chemicals under a high-vacuum environment and maintain such a system with integrity is the chief objective. The article has been necessarily written in a decidedly tutorial tone throughout. It is believed that this work will be especially useful to scientists that are entering this eld, hands on so to speak; however, the methods are organized and introduced with respect to technique, so more experienced workers can proceed directly to a technique of interest. Outline of Contents The High-Vacuum Line Construction General Safety Considerations Cleanliness and Working Efciency Fundamental Techniques Use of Tesla Coil Degassing Simple Distillation Techniques Puried Solvent Storage Purication Chemicals Handling Chemicals Safely Transferring Organometallic Solutions Preparation of Liquid PotassiumSodium Alloy Preparation of Alkali Mirror Ampulization Techniques Simple Ampulization Large-Scale Ampulization Dilution Freeze Ampulization Short-Path Distillation Short-Path Apparatuses Portable Manifold Coerced Distillation Advanced Distillation Apparatuses 6181 6181 6183 6184 6184 6185 6186 6187 6188 6189 6190 6190 6191 6192 6192 6194 6196 6196 6198

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Outline of Contents (Continued) Synthesis of Organolithium Reagents, In Vacuo sec-BuLi Synthesis DLI Synthesis sec-BuOLi Synthesis Polymerization Procedures in Nonpolar Solvents Simple Technique Purge Technique Delayed Ampulization Canadian Technique in Detail Polymerization Procedures in THF Simple Technique Polymerization of (Meth)acrylates Purge Technique Linking Manipulations Using Chlorosilanes: Hellenic Technique in Detail Assembly of the Reactor to Flasks of Collected Active Polymer End-Capping the Active Polymer with Excess Chlorosilane Removing Excess Chlorosilane Titration of the Active Polymer into Stoichiometric Chlorosilane Final Linking Manipulations

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much more macroscopic level: a sh has greater difculty swimming upstream than downstream in a swift current. Here then is a molecular case in which gas molecules face an analogous obstacle.) The entire vacuum system is constructed from glass and mounted securely to a stainless steel frame. We have had reasonable success with the employment of highvacuum stopcocks constructed of a glass channel and Teon piston; the seal between the upper glass barrel of the stopcock and the piston is made by an o-ring, itself sheathed with Teon, which may be very lightly greased for both seal and lubrication. The working manifold is approximately 1.52 m long because it becomes more awkward to work if the vacuum ports are spaced more closely than 30 cm apart. Apparatuses and asks are docked to the vacuum line through the use of complementary ground glass ttings and high-vacuum grease. General Safety Considerations

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Diffusion Pump The diffusion pump uid of choice, historically, has been mercury, and we have traditionally used mercury diffusion pumps ourselves. (Mercury is a heavy metal; therefore, a stream of its vapor has a large momentum that is desirable in an application such as this. Moreover, mercury does not have a high afnity for organic compounds that may be allowed to sweep through the pump.) However, because of the health risks of mercury, we are currently striving to methodically replace them with less hazardous options. We have learned through practice that oil-based diffusion pumps can work just as effectively, and we are presently running trials of two different geometries of glass diffusion pumps, both of which allow access to their interior, thus permitting the changing of oil as needed. Glassblowing repairs to the vacuum line must never be attempted in the region of the diffusion pump while the pump is hot; after it has cooled, blowing must never be provided from the mouth. A hand-held T tube may be used, which has a lightly pressurized inlet of nonammable gas (compressed air or nitrogen), an exit plumbed to the system being blown upon, and a side valve that is opened or closed easily with the use of the blowers thumb. If mercury is selected, then containment of the mercury is essential. It should be kept in mind that there are actually quite a few different geometries of mercury distillation pumps, and it is important to select one with good condensers. Often it is desirable to add an extra condenser to the exit (high-pressure side) of the diffusion pump to help prevent the sweeping of mercury from the pump. A surrounding catch pan, able to withstand the temperature of the hot mercury in the event of a breakage, is also a good idea. The traps must be vigilantly lled, with liquid nitrogen on the low-pressure

HIGH-VACUUM LINE
Construction Two pumps working in series, such as depicted in Figure 1, allow the attainment of a very high vacuum. The pressure in the working high-vacuum manifold can be several orders of magnitude lower than the lowest pressure achievable by the mechanical pump alone. In the 1700s, Bernoulli understood that particles in ow exert a lower transverse pressure than particles in a stationary state. Today, by exploiting this same principle that gives an airplane wing its lift or that allows a simple laboratory water aspirator to provide a modest suction, the diffusion pump can entrain gaseous particles and direct them toward a mechanical pump. The diffusion pump sets up a stream of vapor (the diffusion pump uid). As gases diffuse from the vacuum line into the body of the diffusion pump, they are not rebounded in the same way as from the walls of the glass manifold elsewhere. Rather, here they encounter the stream of diffusion pump uid, in its vapor state and in a motion that is away from the manifold. Thus, gases are swept toward the mechanical pump and prohibited from returning. The diffusion pump uid itself has a high enough boiling point that it may be contained and continuously recycled through cleverly located condensers. (In a purely tutorial note, the principle of the vacuum mechanism is quite easily understood through the use of a metaphor on a

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Figure 1. High-vacuum line.

side and dry ice on the high-pressure side, for the mercury to be safely isolated from the working vacuum manifold and the mechanical pump and the synthesist himself. The diffusion pump must never be heated if the stopcocks isolating the pump are closed for a long period, the mechanical pump is closed, or there is a danger of the water condensers being closed. The risk is that the mercury can become superheated, in which case a sudden decrease in pressure or opening of water ow would lead to a potentially catastrophic event. For the sake of completeness, realize that it is possible to obviate the diffusion pumping system altogether. A turbo molecular pump is able to deliver the same vacuum capability. Under the best circumstances, this type of pump could be considered the safest option. Nevertheless, such pumping units are exceedingly delicate and do not suffer careless use (e.g., accidental in-streaming of gas) without great expense. Furthermore, contamination with chlorosilanes, commonly used in anionic polymerization, can severely damage these pumps. For these reasons, we do not use turbo molecular units ourselves.

It is necessary to clamp all asks and apparatuses that are docked to the line. Many accidents can be avoided if the synthesist keeps the following simple but often overlooked wisdom in mind at all times: vacuum is not a force. If the sum of an objects weight and its internal pressure exceeds the net atmospheric force pushing it up into the vacuum dock at any instant, then it will fall if it is not clamped and will shatter if made of glass, releasing dangerous chemicals into the laboratory environment. Internal Pressures of Closed Systems Keep in mind also that the vacuum line is not designed to withstand internal pressures greater than the surrounding atmosphere. All compounds must be kept below the temperature at which they would boil under ambient conditions, at all times. Gaseous monomers such as butadiene are best collected, off the vacuum line, to a chilled ask in the hood; subsequent transfer to the vacuum line, with an appropriate cold bath already prepared, is then safer. When chilling asks and traps with liquid nitrogen, do not allow them to remain open to the atmosphere for an extended period (of even several minutes) and then close them. Oxygen can condense inside the container: the result is potentially explosive. In some procedures, it is necessary to provide a ow of inert gas to the vacuum manifold. A twin bubbler

Use of Clamps The vacuum line must be clamped securely to the steel frame. Clamps should be used generously around all places where a force may be applied to the vacuum line: traps, vacuum ports, and stopcocks.

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Figure 2. Bubbler for safely pressurizing the vacuum manifold.

such as that depicted in Figure 2 works very well. Inert gas may be fed through the top and delivered to the vacuum line through one of the bubblers. The second bubbler provides a vent to the room. The ow of gas is easily monitored as the stopcock to the vacuum line is carefully opened. Cleanliness and Working Efciency The vacuum line must be kept clean or its efciency is greatly compromised. The result of a messy vacuum line is at best a waste of time in waiting for desired vacuum levels to be achieved and at worst a compromise to the integrity of all synthetic experiments conducted through its use. The mechanical pump must be strong and in good working order and should have its oil changed once per month when the vacuum line is in daily use. If it is suspected that a reactive compound has been permitted into the pump (e.g., a monomer or chlorosilane), then the pump oil must be changed immediately. Also realize that if there is mercury in the mechanical pump, then there is mercury in the room. The vacuum manifold should be kept free of dust and grease because these materials will simply attract and cling to anything that is being distilled through the vacuum line. Once in a while, it is wise to clean the entire manifold. To open the line and allow it to soak is the easiest and rst approach. Aqueous alkali solutions tend to work well at dissolving small quantities of silicone grease. Solvents such as tetrahydrofuran (THF) are also useful for most organic compounds. A more drastic, but once in a while necessary, approach is the use of HF. It is recommended that this be done only by two persons working together; moreover, this method should not be attempted by someone

inexperienced or uncomfortable with the use of HF because its misuse is life-threatening. It is, however, one of the most effective methods of cleaning intricate glassware. The vacuum manifold should be cut free from the upper glass plumbing and taken to a well-ventilated location where there is running water available. There it may be rinsed carefully with HF by the rst person while the second person keeps water running continuously over the rst persons hands and the outside of the manifold. The manifold must be well rinsed and should be allowed to air-dry for 1 day before any glassblowing reassembly is performed. Because it is so difcult to clean the vacuum manifold, the best method is to keep it clean. Use short-pathdistillation techniques. It is possible to use a portable liquid-nitrogen trap in some cases, below at the vacuum port, to trap things before they can enter the manifold. It is recommended that the vacuum manifold be allowed to continuously pump for 24 h after work with monomers or other compounds of low volatility. Calcium hydride must be used to dry most materials; however, when it is employed to dry large quantities of hydrocarbon solvent (several hundred milliliters of benzene or hexanes at a time), our recommendation is to distill the solvent off the vacuum line (conventionally) and simply keep it capped until it is needed. Then it may be degassed over the subsequent chemical treatments. These solvents are not appreciably hygroscopic, and large-scale distillations are very difcult to accomplish without CaH2 dust being swept into the vacuum manifold. The use of splashguards is optional over solvent reservoirs (see Fig. 3). Whether or not they are used, it is best to avoid bumping solvent out of the reservoirs. It is usually very difcult to avoid bumping solvents into the vacuum

Figure 3. Splashguard used to keep the main vacuum manifold clean.

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Figure 4. Locations at which the pressure can be checked inside the vacuum line.

line if the reservoirs are more than half full, so it is wise to use a vessel with a capacity well exceeding the needed amount of solvent. Stir the reservoirs briskly and open the stopcocks slowly to see how the solutions will behave.

FUNDAMENTAL TECHNIQUES
Use of Tesla Coil The Tesla coil is a very convenient tool for checking the level of the vacuum in the vacuum line. The Tesla coil is noisy when held near or touching a vacuum manifold at a pressure achieved by the mechanical pump (see Fig. 4, point A). If the diffusion pump is working well, the coil becomes silent on the high-vacuum side of the diffusion pump (point B). Opening a system to the vacuum line

allows gases and volatile compounds into the vacuum manifold. The Tesla coil is thus noisy upon the opening of a new system to the vacuum line and becomes quiet as molecules are pumped out of the line by the diffusion pump. It is possible to distinguish whether they are gases or volatile organic compounds by listening to the quality of the vacuum on both sides of the liquid-nitrogen trap. Gas molecules pass through the trap and are thus evidenced by noise from the Tesla coil on both sides of the trap (B and C). Solvent molecules, contrarily, are captured there and produce noise only in the vacuum line on the near side of the trap (C). Degassing A liquid system is degassed on the high-vacuum line through an iterative sequence in which dissolved gases

Figure 5. Illustration of a simple distillation (see the text for explanations).

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Figure 6. Solvent-holding vessel.

are repeatedly permitted the opportunity to exit the system. A round-bottom ask is attached to the vacuum line, and the stopcock is opened to the vacuum for a few seconds until the liquid begins to bubble, at which point the stopcock is closed. The following sequence is now repeated: (1) freeze the liquid, (2) open the stopcock to the vacuum line for a couple of minutes, (3) close the stopcock, and (4) thaw the liquid and stir it briskly for a couple of minutes. Each time the liquid is refrozen, the equilibrium is shifted so that dissolved gases may escape and be removed by the vacuum pump. A system being degassed is commonly pumped in the frozen state until the Tesla coil is silent on the far side of the liquid-nitrogen trap, at which point the stopcock is closed and the liquid is thawed and stirred to adjust the equilibrium. A system may be judged to be well degassed if, at the rst moment of opening the equilibrated system to the vacuum pump, there is no noise from the Tesla coil at point B.

vent travels from the source to the destination without condensation ever occurring in the manifold. Generally, liquids that boil below 100 8C under ambient conditions are distilled easily at room temperature with the high-vacuum manifold. Solvents that are less volatile may still be collected through the vacuum manifold, but it is usually best to distill only to an adjacent vacuum port. An illustration is given in Figure 5. Here a source ask is degassed, and stopcock E is closed. A destination ask is evacuated by the opening of stopcocks D and F until a high vacuum is achieved. D is closed. The destination ask is supplied with a cold bath (conveniently 78 or 196 8C), and the source is supplied with a room-temperature bath and stirrer. E is carefully opened. The liquid is collected to the destination. During the distillation, it is often necessary to supply heat to the source; the desirable condition is to keep it at room temperature but not let it become warmer than the vacuum manifold or else condensation will occur throughout the vacuum line. After the distillation, E is closed. The destination is allowed a few minutes to become cold and then is degassed by the opening of D. Finally, F is closed, and the frozen liquid is thawed and stirred. If the source is not already well degassed, degassing may be accomplished during the beginning of the distillation procedure without the source being frozen. A very

Simple Distillation Techniques With ambient gases out of the way, the remaining atmosphere over a liquid in a closed high-vacuum system is simply the vapor pressure of the liquid itself. By the chilling of the destination to which the solvent must be collected, the pressure is reduced there, and the sol-

Figure 7. Reservoir for the long-term storage of solvents.

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Figure 8. Handling organometallic solutions: step I.

small quantity of liquid is collected to the destination by boiling for 520 s, and E is closed. The liquid in the destination ask is frozen, and the system outside the source (that region to which the gases will be driven) is degassed by the opening of D. When a good vacuum is achieved (Fig. 4, check point B with the Tesla coil), D is closed, and the distillation is resumed. By the repetition of this iteration several times, a large quantity of liquid is easily degassed without any need of freezing it at the source. When the system is silent according to the Tesla coil at point B, upon the rst opening of D, the distillation may be allowed to progress without interruption. The use of CaH2 is attended by the evolution of gas so that even if the system has been degassed earlier, it will likely be necessary to temporarily halt the distillation of a large quantity of solvent from CaH2 and degas the system to maintain a high distillation rate.

Puried Solvent Storage Solvents are stored at a vacuum port for up to several weeks with a seal of high-vacuum grease. A cylinder such as the one shown in Figure 6 is very convenient because it can be calibrated; therefore, known amounts of solvent are out-distilled with good accuracy. The bottom of the cylinder must be slightly rounded for safe use at reduced pressure. Generally, the greased vacuum joint will last with integrity for 13 weeks, depending on the nature of the solvent. Optionally, a room-temperature water dish may be placed outside the cylinder for long periods of waiting; through the simple evaporative action of the water, the solvent inside the reservoir can be kept a degree or so cooler than the vacuum manifold (and the greased union), with the effect of retarding solvent migrating into the grease and compromising the seal. Alternatively, a specialty cylinder may be fashioned such as the one shown in Figure 7. The glass side tube

allows the introduction of purication chemicals and is subsequently sealed. Because this cylinder is tted with a stopcock of its own, it may be safely removed from the vacuum port without risk to the integrity of the contents. The grease is then easily refreshed or space is freed for the establishment of an alternative working system upon the manifold. Several points are important in the use of large reservoirs of solvent. First, vacuum distillation does not behave at all as a conventional distillation. In a conventional distillation, the source is heated steadily until its pressure nally exceeds the atmosphere above it; the molecules at the lower surface of the reservoir are supplied with energy, and the bubbles therefore form there: the distillation is easily controlled. In a distillation at the vacuum line, the pressure in the system is rapidly reduced and remains somewhat uctuant in nature. The result is that bubbles form suddenly and anywhere in the reservoir; solvent is easily bumped and splashed into the vacuum line. This is undesirable because, although the solvent is volatile and easily removed, the chemical purication reagents are not. The reservoirs should not be lled more than half full, and they must be stirred briskly and opened to the vacuum manifold very carefully to see how the solutions will behave. Vacuum distillations must be carefully tended. Often, changes in temperature of the source have a great effect on the rate of distillation, and the destination must be regularly replenished with either liquid nitrogen or dry ice. Often, doing several things at once means that the distillation will take several times as long; hence, no time is saved. Finally, the thawing of a frozen liquid in a reservoir is quite dangerous because there is a potential for the ask to break. There is, of course, a change in density associated with any freeze/thaw process. An empty bath may be set to house the reservoir, and tepid water may be poured, in one single addition, over the entire ask so that the contents are freed from the surface of the glass from the top down. If water is added too slowly or added only to the bottom of the reservoir, it is much more likely that a rupture of the ask will occur.

Figure 9. Handling organometallic solutions: step II.

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Leftover sodium is quenched by its reaction with alcohol in the hood. Hydrogen gas is evolved. The reaction with methanol is dangerous unless the metal is already under another organic medium that will dilute the methanol. Isopropyl alcohol is a safer choice. Again, the reaction is heterogeneous, and it may be necessary to stir the solution to ensure that the deactivation is safely accomplished. Potassium
Figure 10. III.

Handling organometallic solutions: step

PURIFICATION CHEMICALS
Handling Chemicals Safely Calcium Hydride This is the most commonly used drying agent employed. It is obtained in lumps and is best ground into a ne powder just before use because it readily reacts with moisture in the air. It can often be reused several times, especially in cases in which it is used to treat nonhygroscopic solvents and in systems that are kept closed from the atmosphere. The leftover CaH2 is deactivated with water before its disposal, but the reaction is too violent to simply add water to the chemical. One method is to pour the chemical over ice. Another method is to make a slurry of the powder in alcohol (e.g., ethanol) and carefully add water (or dilute aqueous HCl) dropwise. Either of these deactivation methods is still quite vigorous, is accompanied by the evolution of ammable hydrogen gas, and should be accomplished in the hood. Because the reaction with CaH2 is heterogeneous, the deactivation is most safely accomplished with stirring.

This alkali metal is also somewhat regularly used and requires even more care than sodium. It is received as chunks under a blanket of mineral oil. The oil may be removed by rinsing the metal with hexane, and it may then be stored in a tightly capped jar under hexane; it is strongly urged that the hexane should be rst distilled from CaH2 before use in this manner. Potassium must never be allowed to dry in the room atmosphere. It will spontaneously ignite in the presence of air. It reacts explosively with both water and alcohol. Leftover potassium must always be blanketed with a large quantity of hexane (or, for periods of longer storage, heptane, which has the benet of being less volatile), and unused material may be quenched in the hood by the careful dropwise addition of alcohol to the hexane solution. Lithium Lithium is used primarily in the synthesis of organolithium reagents and should consequently be kept clean as possible. We have had good success in the use of a dry powder or granular form that contains $0.5% Na. It is best to open, handle, and transfer the metal only under a continuous blanket of inert gas. Nitrogen is adequate, but argon is a better choice.

Sodium This reagent is the most commonly used alkali in anionic polymerization purication procedures. It is obtained in large solid sticks and stored in grease-sealed desiccators. It may be cut into small pieces in the room atmosphere with a blunt stainless steel knife. It quickly builds up a coating of oxide, so it should be protected from exposure to the air for periods longer than 1 min. In cases in which sodium without a coating of oxide is desired, the metal may be cut under a blanket of hexane in a glass dish and allowed to dry under vacuum or in an inert gas ow.

Figure 11. Handling organometallic solutions: step IV.

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familiarization with cannula techniques18 would indeed greatly benet the synthesist, this description is intended only to narrowly illustrate the effective transfer of such a compound to a vacuum system. A step-by-step account is provided here and is illustrated in Figures 812. I. The bottle of the reagent solution is kept in a bottle equipped with a septum. When the reagent is needed, the septum is pierced with a needle that can deliver a light pressure of inert gas. A dry needle-tipped syringe is then also inserted through the septum (Fig. 8). II. The solution is drawn into the syringe. Tilting of the bottle may be necessary (Fig. 9). III. The ask or apparatus requiring the solution is already prepared and dried and is under vacuum; the stopcock to the vacuum manifold is now closed. The solution is injected by piercing a rubber septum with the needle of the syringe. Because the system is under vacuum, the contents are spontaneously inhaled into the ask (Fig. 10). Care should be taken to exclude as much air as possible from the system: after the solution has been drawn into the ask, the syringe is immediately withdrawn from the septum; otherwise it will continue to leak. A small quantity of grease may be applied to the septum. IV. The constriction of the side arm is rinsed free from any residual organometallic compound. A towel strip dipped in liquid nitrogen and briey wrapped around the side arm effects this: the blanketing solvent (e.g., hexane) reuxes quite easily from room temperature because the system is under reduced pressure (Fig. 11). In the event that a little air has been allowed into the system through a clumsy transfer, the vacuum may often be enhanced by the opening of the ask to the main vacuum for 2 s. The constriction should be rinsed several times. After the constriction is clean, it is sealed, and the side arm is detached through the use of the hand torch.

Figure 12.

Handling organometallic solutions: step V.

Excess lithium is extremely reactive when it is in a powder form. It may be quenched in a manner similar to that of potassium. Organometallics Butyllithium (BuLi), dibutylmagnesium (Bu2Mg), and alkylaluminums (Alk3Al) are received as hydrocarbon solutions in bottles protected with a sureseal cap. They are obtained from the bottles by using needle-transfer techniques in one of two ways. In the rst method, a dry needle-tipped syringe is lled with at least as much inert gas as the amount of organometallic solution desired, the septum is pierced, the inert gas is injected into the bottle, and the solution is withdrawn. In the second method, the bottle is pierced by a needle that is plumbed to a ow of inert gas; with a needle-tipped syringe, the septum is pierced a second time, and the solution is withdrawn under the compensating pressure of inert gas from the rst needle. The second method is the better technique. The handling of such reagents is illustrated later in greater detail. The quenching of pyrophoric organometallic compounds is extremely dangerous and should be accomplished in the hood, with the shield drawn. Concentrated solutions may often not be quenched without the violent attendance of re; therefore, if the reagent is not already diluted with leftover solvent or monomer, then it should rst be diluted with a small quantity of hexane. The dropwise addition of methanol is accompanied by the evolution of both heat and gaseous hydrocarbon (e.g., butane). Transferring Organometallic Solutions Organometallic reagents are routinely employed in the course of anionic polymerization methodologies. BuLi, Bu2Mg, and Alkyl3Al solutions are steadfastly protected from the atmosphere with appropriate blanketing and transfer techniques. Because they are extremely reactive (pyrophoric), it must never be forgotten to handle them with respect, for the sake of both the experimentalists safety and the reagents potency. Although a thorough

Figure 13. Preparation of the K/Na alloy: step I.

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II. K and Na metal are cut into small pieces under a blanket of dry hexanes. The quantity of alkali metal used is adjusted, according to the eye, so that the ratio of K to Na is about 3. For the purpose of making the alloy, any large accumulation of oxide coating is best cut off the surface of the metals (Fig. 14). III. Under a stream of inert gas delivered from the opposite opening of the apparatus, K and Na are transferred to the ask (Fig. 15). The hexane is allowed to evaporate from the metal under a slow ow of inert gas for about 10 min. IV. The apparatus is closed. The following series of events must be accomplished in quick succession: (1) the inert gas ow is stopped; (2) from a remote location (preferably through the vacuum line, for a greater distance), a blowpipe is tted for use upon the apparatus; (3) the glass tube is sealed and blown round (it is important to not blow too much, but the entry needs to be both sealed without a hole and stable to withstand outside atmospheric pressure); and (4) the apparatus is evacuated to the vacuum. V. The ask is gently heated with a soft moving ame from a hand torch (Fig. 16). K will melt before Na melts. As soon as it can be seen that K is beginning to melt, the heating is stopped. VI. With a horseshoe countermagnet, the internal glass stirring bar is moved about, agitating the metal contents (Fig. 17). K nishes melting. Na also begins to melt and is dissolved into the molten potassium. After all of the solid chunks of metal have been incorporated by hand, the horseshoe magnet may be removed and replaced by a magnetic stirring plate.

Figure 14.

Preparation of the K/Na alloy: step II.

V. The stopcock to the vacuum manifold is now reopened, and the solvent is stripped from the organometallic reagent. It is often not necessary to remove all traces of the solvent from the reagent as long as all gases have been removed. The ask is now prepared for subsequent in-distillation of the solvent or monomer to be thus treated (Fig. 12). Generally, the organometallic stock reagents are kept in the refrigerator after opening. A glovebox is alternatively appropriate. These reagents often become cloudy after opening several times; however, their potency is generally retained to be effective as purication agents. (This can indeed be veried by the careful quenching of the material after its use in the hood.) Once the septum has been pierced the rst time, it begins to deteriorate slowly; thus, we can extend the life of the reagent by insisting upon inert gas blanketing, keeping the solution away from direct contact with the septum, and also placing a small fresh piece of folded paralm over the septum (underneath the screw-on cap) after each use. In this way, the reagent is preserved for quite a long time and for repeated sampling. Preparation of the Liquid PotassiumSodium Alloy The K/Na alloy is prepared in the laboratory. Because it is an extremely powerful reducing agent, it must be prepared, handled, and nally quenched with utmost care in a manner similar to that previously described for the handling of K metal. A step-by-step description of the preparation is given here and is illustrated in Figures 1317. I. A ask or apparatus is prepared from all-glass construction and tted with a glass exit/entry tube. The apparatus is docked to the vacuum line, evacuated, ame-dried, and checked for integrity by using the Tesla coil. It is then repressurized with a blanket of inert gas (Fig. 13).

Figure 15. Preparation of the K/Na alloy: step III.

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II. The alkali metal is introduced to the side tube under a light ow of inert gas. If hexane is used as a blanket (mandatory for K, optional for Na), then it must be allowed to evaporate for several minutes under the stream of inert gas. III. The apparatus is closed. The following series of events must be accomplished in quick succession: (1) the inert gas ow is stopped; (2) a blowpipe is tted for use upon the apparatus at the opposite end of the alkali metal inlet; and (3) the glass tube is sealed and blown round (it is important not to blow too much, but the entry needs to be sealed and stable to outside pressure). IV. As soon as the glass has cooled, the apparatus is inverted back to its right-side-up orientation, docked to the vacuum line, and evacuated. The apparatus is pumped until a good vacuum is achieved (see Fig. 19). V. The alkali metal and glass arm are heated with a hand torch. The torch is adjusted to maintain a large, diffuse blue ame. The torch is moved continually so that the entire glass arm becomes very hot, and the alkali metal is distilled under dynamic vacuum to the ask. It is important to keep the torch moving because the ame must be adjusted to a temperature at which the glass would melt if it were held still. VI. Optionally, the glass side arm is detached by sealing the constriction nearest the ask. The reward is a mirror coating the ask, with the appearance of a Christmas ball (Fig. 20).

Figure 16.

Preparation of the K/Na alloy: step V.

VII. The apparatus may be closed from the vacuum line. The contents are stirred for about 1 h until a very smooth, homogeneous alloy is formed. The alloy remains a liquid at room temperature. If the vessel to contain the alloy is tted with a stopcock, we can instead introduce the solid pieces of K and Na through the stopcock barrel, thereby avoiding the risk of sealing and blowing the glass side arm, as directed previously. Keep in mind that the K/Na alloy is potentially one of the great re dangers in the laboratory. The previous description is essentially an account of how to prepare the alloy; the decision of when to employ it is left to the judgment of the experimentalist. A more benign chemical substitute is diphenylhexyllithium (the adduct of BuLi and DPE), which works well as a drying agent for ethereal solvents.

AMPULIZATION TECHNIQUES
Simple Ampulization A volatile compound is distilled through the vacuum manifold into ampules and captured by sealing the con-

Preparation of Alkali Mirrors Alkali mirrors must be freshly prepared, under vacuum, in the apparatuses requiring their use. Na mirrors are the most common (although K mirrors can be just as easily prepared). The main advantage of a mirror is that it has an extremely large solid alkali surface area of very high purity that cannot be otherwise obtained. A step-by-step procedure is given here and aided by Figures 1820.

I. A ask or apparatus is prepared from all-glass construction and tted with a glass exit/entry tube (see Fig. 18). The apparatus is docked to the vacuum line, evacuated, ame-dried, and checked for integrity by using the Tesla coil. It is then repressurized, removed from the vacuum line, inverted, and blanketed under a ow of inert gas.

Figure 17.

Preparation of the K/Na alloy: step VI.

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Figure 18. and II.

Preparation of an alkali mirror: steps I

Besides the apparatus breaking because of gross mechanical failure of the glass, there is another potential reason for failure of the apparatus. If there is a small quantity of moisture in the apparatus when it is rst opened to the vacuum line, sudden evaporation can cause the water to freeze inside the break-seals and rupture the seals. To remove much of the water, the apparatus can be dried in an oven at 120 8C. Otherwise, it is wise to warm at least the break-seals with a soft blue/ yellow ame of the torch and to keep them warm during the initial evacuation of the apparatus. In the sealing of constrictions, a sharp, focused blue ame must be used. It is necessary to heat all sides of the constriction equally or it will collapse asymmetrically and possibly implode. If the back of the constriction cannot be heated, then do not heat the front either; deliver the heat tangentially left and right. Keep in mind that heat rises. As the glass softens, pull the ampule gently to help the glass collapse uniformly. Back off with the torch at the end and polish the seal for a few seconds at a lower temperature. Large-Scale Ampulization It is sometimes necessary to ampulize a large quantity of a compound for a single use. Alternatively, it may be desirous to capture a reagent on a large scale so that small, later decided quantities may be easily taken as they are needed. An apparatus suitable for these types of needs is shown in Figure 22. This ampulization technique is particularly appropriate if the purication of a compound is difcult and if it is desired to purify an extra amount for easy later use. It is also useful in the case of a reagent that, once opened, is best captured and sealed under vacuum for reasons of wishing to retain the integrity of the reagent.

strictions with a hand torch. A basic all-glass ampulization apparatus is shown in Figure 21. This type of apparatus is useful for the collection of small quantities of solvents such as Lewis additives or alcohols. Briey, the stepwise sequence to be used is as follows. I. The apparatus is evacuated on the vacuum line and veried for integrity by use of the Tesla coil. The ampules are ame-dried and pumped until a high vacuum is persistent. II. The compound is collected to the apparatus with a simple distillation through the manifold. Because of the geometry of the ampule, a cold bath cannot be used. Following are two convenient methods of chilling the ampules: (1) with a small cloth towel strip dipped in liquid nitrogen, the ampule is briey cloaked and chilled; or (2) with a small bath of dry ice and isopropyl alcohol beneath the ampules, the ampules are bathed with the slurry with a small brush, the drip-off below the apparatus being caught with the bath. III. The ampules are taken by being heat-sealed and detached from the apparatus at the constrictions. Naturally, as many or as few ampules as desired may be assembled in an apparatus. Apparatuses tend to become clumsy and easier to break if there are more than 10 ampules. It is wise to not build an apparatus larger than it needs to be. We can calibrate the ampules by lling them with a known quantity of deionized water and placing a scratch on the glass before assembling the apparatus.

Figure 19.

Preparation of an alkali mirror: step IV.

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Figure 20.

Preparation of an alkali mirror: step VI.

For example, commercial organolithiums often lose their potency once the seal is compromised the rst time. Transfer of the organolithium reagent into an all-glass apparatus and degassing are wise if it is desired to use the reagent repeatedly (for use as an initiator, for example, where a quantitatively controlled portion is important). The apparatus in Figure 22, as depicted, is suited for an in-distillation of reagent through the vacuum manifold, but a small constricted entry can easily be added to the main ask (such as shown in Fig. 10). After drying the ampulization apparatus, the concentrated reagent may be injected. Optionally, the apparatus may be rst repressurized with inert gas, and a carefully controlled long-needle delivery of the reagent may be made to the ask. Small bottles of chlorosilanes are also best puried once they are opened. Otherwise, the rubber-lined caps tend to degrade rapidly after they are pierced.

that are deleterious to the Si Cl bond, including glass surface contaminants such as Si OH, are given an opportunity to deactivate with a small sacricial quantity of this silane. Experimentally, a small quantity of (CH3)3SiCl is introduced to the apparatus and used to completely wash the inner glass surface (liquid nitrogen/ towel strip); the contents are then pumped, without ame drying the apparatus, until a good vacuum is achieved. The apparatus is then ready to capture the chlorosilane to be employed experimentally. When ampules of the reagent are taken, it is rst necessary to rinse the constriction if the diluted reagent is nonvolatile (e.g., organolithiums will not move out of the way of the ame but rather will stay and decompose on the surface of the glass). If the constriction is rinsed, be aware that the concentration will be affected. Gently back-distilling the amount of solvent used in rinsing to the cylinder, before detaching the ampule, will ensure a steady concentration in the apparatus. If the contents of the apparatus are all volatile, simply prewarm the constriction gently with the torch to allow all reagents to move out of the way before detaching the ampule. Freeze Ampulization An ampulization apparatus of alternative geometry, depicted in Figure 24, permits the freezing of a volatile

Dilution A typical dilution apparatus is shown in Figure 23. With an apparatus such as this, an ampule of a concentrated reagent may be diluted with a solvent obtained from a puried reservoir elsewhere docked to the vacuum manifold. The apparatus may be purged with BuLi by the attachment of a purge section. Generally, purging is necessary in the case of preparing dilute organolithium solutions of concentration precision or in the dilution of multifunctional organolithiums. Otherwise, it is simply advised to allow a long pumping time under the vacuum and to ame-dry the apparatus repeatedly. Silanization is an alternative to purging and is sometimes prudent in the use of multifunctional chlorosilanes. When the chlorosilane is used in concentrated (excess) amounts, it is expedient to simply use the apparatus. When a chlorosilane must be repeatedly transferred to additional apparatuses or diluted for stoichiometric usage, it is best to rst silanize the apparatus. (CH3)3SiCl is the chlorosilane used for this purpose. Any impurities

Figure 21. Simple ampulization apparatus.

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Figure 22.

Large-scale ampulization apparatus.

compound before it is detached and sealed into an ampule. This technique is particularly advised in the collection of monomers but can be used for the collection of any volatile compound that is unstable in the presence of heat. A general stepwise experimental procedure is given here. I. The apparatus is evacuated on the vacuum line, and the ampules are ame-dried and pumped until a high vacuum is persistent. II. The compound is collected to the apparatus by the performance of a simple distillation through the manifold. After the compound is collected into the ampule, it may be thawed to measure the volume collected; adjustments can be made by further in- or out-distillation. III. The source is closed. The ampule is frozen at 196 8C, and the apparatus is opened to the main vacuum to permit a nal degassing. IV. The ampules are taken by being heat-sealed and detached from the apparatus at the constrictions. It is important to ampulize monomers in this way both because they are unstable and because they must be

exceedingly pure to obtain high-molecular-weight polymer. (The propagation step must occur many times unambiguously.) It is advised to give the compounds several minutes to become cold and to leave the main vacuum open during the detachment of the ampules. Moreover, after the ampule is sealed, the contents should be kept frozen until all of the glass has cooled to room temperature. Thaw the ampules and let them come to rest at 20 8C (or whatever temperature is required for the density value being used) before taking a volumetric measurement. Otherwise, for long experimental periods, keep them cold as necessary. Volatile monomers (e.g., isoprene, bp 35 8C; cyclohexadiene, bp 80 8C) are easily collected through the vacuum manifold. Exceedingly volatile monomers (e.g., butadiene, bp 5 8C) may be ampulized; however, they must be diluted in the ampule to reduce their pressure. The monomer is collected and measured at a cold temperature at which a density value is available. Subsequently, it is frozen, and the solvent is collected above the monomer; the ampule is degassed, detached, cooled, and carefully thawed. Freeze ampules may be constructed in several stages of round tubing (see Fig. 25). This permits collection of rst a small quantity of one compound, with a reason-

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Figure 23.

Dilution apparatus.

able volumetric accuracy, and subsequently a large amount of another compound. For example, in this way both a monomer and the solvent required for its polymerization may be captured in one ampule. The procedure to be followed in a compound freeze ampulization is essentially the same as that described in a simple freeze ampulization.

SHORT-PATH DISTILLATION
Short-Path Apparatuses Compounds that have a low volatility (usually monomers) can still be transported with distillation techniques under vacuum. It is best to require them to travel only short distances. Often they must be heated at least slightly above room temperature to increase their vapor pressure; this leads to a more global condensation behavior such as is observed in conventional distillations. This behavior is a good reason to restrict the distillation path as much as possible. Specialized short-path apparatuses are extremely useful. The following detailed procedure and the support-

Figure 24. Freeze-ampulization apparatus.

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III. The entry tube is closed with a septum, the apparatus is redocked to the vacuum line, the contents of the apparatus are frozen, the apparatus is evacuated, and the entry tube is sealed with the torch. IV. The contents are degassed, thawed, and allowed to stir over CaH2. V. The monomer is distilled to the preliminary ampule; a slightly warm water bath may be used at the ask as necessary, but it is best to use no more heat than is required. A brief degassing immediately beforehand greatly helps to promote transport of the compound. The ampule is frozen well and detached from the apparatus with a hand torch. VI. With the preliminary ampule collected from the drying procedure, a nal purication apparatus is assembled. This apparatus is docked to the vacuum line, evacuated, veried for integrity, and dried.
Figure 25. Freeze ampulization: compound (dilution) ampule.

ing illustrations given in Figures 2628 describe a twofold (two distillations and two apparatuses) purication. I. An all-glass drying apparatus is prepared, evacuated, dried, veried for integrity, and repressurized. II. A Teon stirring bar, CaH2, and the monomer are introduced to the apparatus.

VII. The apparatus is closed from the manifold and left under vacuum. Using the side-arm entry, a small quantity of an organometallic solution is injected into the apparatus with a syringe (e.g., the purication of styrene requires the use of Bu2Mg). VIII. By using a towel strip dipped in liquid nitrogen to lightly reux the solvent of the organolithium reagent, the side arm is rinsed in the vicinity of the constriction; the side arm is then sealed with the hand torch, and the solvent is removed by reopening the apparatus to the main vacuum. The apparatus is pumped until a good

Figure 26.

Short-path distillation: drying apparatus.

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Portable Manifold It is possible to do less glassblowing and still keep highboiling compounds out of the permanent vacuum manifold through the use of a portable manifold, which may be easily cleaned and reused many times. Purication asks with complementary connections are needed, but they are recyclable as well. A portable short manifold is depicted in Figure 29. This short cut is a quite viable option for compounds that boil below $200 8C under ambient conditions. Keep in mind that contamination of grease into the nal ampules must be prevented. The less volatile compounds tend to behave much better through the employment of an all-glass path having as little a vertical climb as practical. Coerced Distillation vacuum is achieved and the solvent has been removed to the main liquid-nitrogen trap. IX. The apparatus is closed from the manifold; the seal to the preliminary ampule is ruptured; and the monomer is collected to the ask, where it is frozen. The apparatus is opened to the vacuum line and allowed a nal degassing; the empty preliminary ampule may be detached. The monomer is thawed and allowed to stir over the organometallic reagent. X. The monomer is collected to the nal ampules, using freeze-ampulization techniques. Before the ampules are detached, it is recommended that the entire contents of the apparatus be frozen and the system be opened to the main vacuum in preparation for use of the torch. Distilling compounds that have an exceedingly modest volatility can still be accomplished under high vacuum. An all-glass path, a dynamic vacuum (open vacuum during the distillation procedure), and the use of stronger heat than in routine short-path distillations are requisite; moreover, these compounds are nearly always puried in a manner that only requires one distillation to be performed. Compared with a conventional procedure, which would ordinarily be attended by a great loss of material due to side reactions or decomposition, the boiling point is often diminished by 150200 8C through the use of these techniques. A step-by-step procedure is given presently and is supported by Figures 3033. I. The apparatus is assembled according to the illustration in Figure 30. After the apparatus is evacuated and

Figure 27. apparatus.

Addition of compounds to an all-glass

Figure 28.

Short-path distillation: nal purication apparatus.

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II. The compound to be puried is introduced to the apparatus through the side arm with a needle-tipped syringe (see Fig. 31). The side arm is ideally constructed of a short enough length that the needle can reach through the constriction into the ask and thus facilitate a clean delivery of the material. III. With a clean needle and syringe, the purication agent is added next, dropwise. For example, the purication of DPE and similar compounds is accomplished by the addition of a solution of n-BuLi in hexanes, dropwise, until a persistent vivid red metalation adduct is formed. Note that the addition of reagents to the ask would be uncontrollable if it were under vacuum. After the reagents have been added, the needles are removed from the septum and the inert gas feed is closed. The introduction of a modest amount of vacuum (by the momentary opening of the apparatus to the main vacuum) permits rinsing of the constriction (with a towel strip dipped in liquid nitrogen) should rinsing be necessary before the apparatus is sealed. IV. The side arm is detached. The apparatus is carefully opened to the vacuum with brisk stirring; the vola-

Figure 29.

Portable short-path manifold.

its integrity is established, it is repressurized with inert gas by a feed through the vacuum manifold. A needle through the septum provides a vent from the apparatus after it has been pressurized.

Figure 30. Coerced-distillation apparatus.

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VII. Puried solvent (hexanes) is distilled into the collection cylinder from a reservoir elsewhere docked at the vacuum manifold. This helps both to dilute the compound and to decrease its viscosity. The apparatus is detached from the vacuum line by sealing the opposite constriction (see Fig. 33 to view the apparatus at this point). VIII. The contents are mixed well and split into the ampules. The ampules are nally detached from the remaining apparatus and stored for later use.
Figure 31. Addition of reagents to the apparatus.

Advanced Distillation Apparatuses tile solvent diluent of the organometallic agent is stripped from the solution, and the remaining contents are left to stir under dynamic vacuum for a period allowing the purication to be accomplished. V. The distillation is commenced by raising the temperature of the ask; the vapor pressure of the compound is increased to permit it to reux in the ask. The vacuum is left open during the procedure (see additional notes at Fig. 32). VI. After the distillation is complete, the ask is allowed to cool. The ask and goose-necked distillation path are detached from the apparatus. The apparatuses depicted in Figures 34 and 35 require a more adept glassblowing skill. The payoff of this extra work is the ease with which distillations may be accomplished through their use. The distillations are directed through an all-glass path, which obviates the risk of contamination with vacuum grease; moreover, the compounds are persistently excluded from the vacuum manifold. The experimental procedure to be followed during the purication and ampulization of compounds with these apparatuses is analogous to that previously described for short-path distillation, and so a step-bystep account of the technique is omitted. Figure 34 shows an apparatus intended to be useful for an ordinary short-path style of distillation (i.e., the vacuum is closed

Figure 32. Coerced distillation in progress.

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pound is collected to the ampules. For example, methyl methacrylate can be treated rst with CaH2 and then with Oct3Al with this apparatus. A twofold coerced distillation is accomplished with a minimum of experimental difculty with an apparatus such as that depicted in Figure 35. A difcult compound may thus be distilled twice under a dynamic vacuum. For example, 4-(t-butyldimethylsilyloxy)styrene (a silylprotected para-hydroxystyrene monomer) can be treated with CaH2 and Bu2Mg, sequentially, and nally diluted in hexanes with this apparatus.

SYNTHESIS OF ORGANOLITHIUM REAGENTS IN VACUO

The quality of organolithium reagents is very crucial to successful reproducible polymerizations. In some cases, clean commercial products are available. We prefer to synthesize the following compounds in house, and the necessary manipulative techniques are illustrated through the three specic synthetic examples chosen.
Figure 33. Split-down abdomen of the all-glass apparatus.

sec-BuLi Synthesis This initiator is synthesized through the reduction of sec-BuCl by Li metal according to the following chemical reaction: sec-BuCl 2Li !sec-BuLi LiCl This reaction is accomplished inside an all-glass synthetic apparatus,19 which is shown in Figure 36. The preparation of the synthesis requires previous ampulization of sec-BuCl and purication of hexane. sec-BuCl is

during the distillation). After the calcium hydride and the compound are collected into ask 1, it is sealed from the room and degassed. Next, we seal the glass bridge toward ask 2 with a torch by collapsing the capillary and cutting it gently with a glass rod. Flask 2 is then prepared with the organometallic reagent. At the appropriate time, the seal between asks 1 and 2 is ruptured (this reopens the glass bridge), and the compound is collected to ask 2; after the nal chemical treatment, the com-

Figure 34.

Compound short-path-distillation apparatus.

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Figure 35.

Compound coerced-distillation apparatus.

dried over CaH2 on the vacuum line with stirring overnight, degassed, and ampulized (simple ampulization); subsequently, this ampule is assembled to the vacuum synthetic apparatus. Hexane is left on the vacuum line, over BuLi, in a puried reservoir. Li metal (0.5% Na, powder) is recommended in a quantity at least sixfold that of sec-BuCl. A convenient recipe uses 10 g Li, 20 mL sec-BuCl (the limiting reagent), and $200 mL hexanes. The full synthesis is now described in a step-by-step account, the text of which is supported pictorially by Figures 3639. I. The apparatus is assembled, as shown in Figure 36, and docked to the vacuum line. Because of the size of the apparatus, the use of several clamps is advisable to stabilize both the upper and lower portions. The apparatus is then evacuated, veried for integrity by use of the Tesla coil, and ame-dried. The apparatus is then carefully repressurized with a blanket of inert gas. II. The lithium is introduced into the apparatus by means of the removable ampule (see Fig. 37). Depending on the physical state of the Li metal, it may be more or less forgiving of the exposure to the room atmosphere. We have had good success in the past with a ne dry Li powder, which must be carefully protected. Recently, we have used more coarse granules (small, dry chunks). Li dispersion in parafn is rather tolerant of the ambient atmosphere for short periods; however, it is later experimentally laborious to strip the parafn away, by the washing with hexanes, and we therefore do not recommend it.

III. After the ampule of Li metal is attached to the apparatus, the inert gas is closed to the vacuum manifold; the apparatus is carefully opened to the vacuum; the Li powder will dance a little as the pressure is reduced; and the apparatus is left to degas until a high vacuum is achieved. IV. BuLi is injected into the purge ask, the side arm is rinsed and sealed, and the apparatus is degassed. V. Hexane is in-distilled to the apparatus, and the apparatus is again degassed. VI. The following sequence is best accomplished somewhat quickly if possible:  The apparatus is detached from the vacuum line.  The hexane and BuLi are thawed.  The apparatus is carefully tumbled in all directions to wash the entire inside glass surface and the Li metal with the BuLi solution.  Li powder is collected out of the ampule and into the reactor, and the heavy wall glass path between the reactor and the ampule is rinsed as well as possible.  The glass entry tube is sealed shut, and the portable ampule appendage is removed from the reactor. The apparatus is now entirely sealed within glass, and there should be no leaking.

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Figure 36.

Vacuum synthetic apparatus for the synthesis of sec-BuLi.

VII. The apparatus is set in a position to reux from the purging recovery ask. The BuLi is thus rinsed from the apparatus and collected back to the recovery ask over a period of several hours. It will take time to collect hexanes above the glass lter in each rinsing iteration, but the reactor and Li must be rinsed well. The intermittent use of a towel strip dipped in liquid nitrogen is helpful. Periodically collect all of the hexane back to the recovery ask, by chilling the ask, to begin a fresh rinse cycle.

VIII. Hexane is carefully distilled to the reactor, and the purging section is detached from the apparatus. IX. Li metal is collected as cleanly as possible to the reactor ask (removed from the path to the sec-BuCl ampule). The reactor is inverted to a position such as depicted in Figure 38. X. The reactor is chilled to 0 8C, and the Li dispersion is stirred briskly. (The reaction is exothermic and must

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Figure 37.

Transfer of Li metal to the apparatus.

be controlled; moreover, the reaction product is not stable at room temperature for long periods.) XI. The seal to sec-BuCl is ruptured; the contents are allowed to gently distill to the reactor over the course of $1 h. Once the contents have been distilled, the reactor is continued with brisk stirring at 0 8C for 4 h. Finally, the reactor bath is packed with ice, and the reaction is left to complete overnight. XII. The reactor is inverted, and the solution is collected through the lter (see Fig. 39). A very clear, pale yellow hue is observed. It is best to let the solution pass very slowly through the lter, to avoid pulling any small Li dust particles through the lter, and to pull the product with the solvent. A cool water bath is both gentle and safe to use (510 8C, keep the level of the bath

below the level of accumulating solution). It is not recommended to rinse the reactor; the solution is simply allowed to collect below in one transfer. XIII. The apparatus is rotated, and the solution is distributed entirely among the ampules. All the constrictions are rinsed simultaneously (in this manner, the concentration is not greatly disturbed), and the ampules are taken. The concentration of the reagent may be roughly established quite easily by use of the sacricial ampule. The ampule is broken open, quenched into a large excess of water, and titrated with HCl to a phenolphthalein endpoint. The Gilman double titration is an alternative.20 In this case, two sacricial ampules are needed; the rst is treated as mentioned previously, and the second is treated as follows: the ampule is quenched into a solu-

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uum line. However, when very dilute solutions of initiator must be used, or when it is best to exclude traces of alkoxide (e.g., titration results of macroanions upon chlorosilanes are very sensitive to aggregation phenomena), then it is best to insist that the reagent be kept as clean as possible.

(1,3-Phenylene)bis(3-methyl-1-phenylpentylidene) Dilithium Initiator (DLI) Synthesis DLI,21 a difunctional hydrocarbon-soluble organolithium initiator, is synthesized through a twofold adduction of sec-BuLi to a difunctional monomer that cannot itself polymerize. The chemical reaction is given here:

Figure 38. Reactor ask in which the chemical reaction between Li metal and sec-BuCl occurs.

tion that contains a reactive electrophile such as benzyl bromide; the product of this reaction is then titrated with HCl to a phenolphthalein end point. The concentration of organolithium is manifested in the difference between the two titration results. In practice, this titration is rarely done in our laboratory. Instead, it is assumed that the results of the simple titration are near the actual value. An ampule of secBuLi is then diluted to a useful concentration, and a title polymerization of styrene is accomplished under strict high-vacuum conditions. The concentration of the initiator is then accurately established based upon the results of this polymerization: Molarity Grams of monomer used=MW of PS Volume of initiator used

where MW is the molecular weight. sec-BuLi is quite stable, sealed in glass under vacuum at cold temperatures. It may often be kept for periods of up to several years at 20 8C. Once the reagent begins to deteriorate (as evidenced by cloudiness or precipitate in the ampules), the decomposition seems to progress further much more quickly. For purposes of routine dilution and transfer to subsequent apparatuses, purging the new initiator apparatus may generally be omitted, provided that the glass is clean and the apparatus is thoroughly dried on the vac-

This reaction is accomplished inside another variation of an all-glass synthetic apparatus,19 which is shown in Figure 40. The preparation of the synthesis requires purication and ampulization of 1,3-bis(1-phenylethenyl)benzene (PEB),22 preparation and ampulization of sec-BuLi, purication of hexane, and purication of benzene. PEB is puried over n-BuLi and collected with a coerced distillation at 140 8C. PEB is used as the limiting reagent, typically on a scale of 0.52 g, depending on need. sec-BuLi is ampulized in a quantity of at least 2.1 equiv of PEB. Ampules of PEB and sec-BuLi are assembled to the vacuum synthetic apparatus. Hexane and benzene are left on the vacuum line in puried reservoirs (over BuLi and PSLi, respectively). The synthesis of DLI is now fully described in a stepby-step account and illustrated by Figures 4044. I. The apparatus is assembled, as shown in Figure 40, docked to the vacuum line, evacuated, veried for integrity by use of the Tesla coil, and ame-dried. The apparatus is left to degas until a high vacuum is achieved. II. BuLi is injected into the purge ask, the side arm is rinsed and sealed, and the apparatus is degassed.

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adduct is insoluble with time and stable at room temperature. XI. The apparatus is inverted (see Fig. 42).

XII. The hexanes are collected to the bottom recovery ask. Excess sec-BuLi (or any monoadduct byproduct) is soluble and will be removed from DLI in this manner. A sparing solubility of DLI will give the hexane a deep red color, but this minimal loss of DLI is unimportant. The recovery ask is detached from the apparatus. XIII. The apparatus is reattached to the vacuum line by means of the break-seal appendage (see Fig. 43). After a high vacuum is obtained, the seal is ruptured. XIV. Benzene is distilled into the reactor, and the apparatus is detached from the vacuum line. XV. DLI is dissolved in the benzene (see Fig. 44 to view the complete remaining apparatus at this point). The solution is collected across the lter and to the nal apparatus. The apparatus is rinsed well with the benzene with a liquid-nitrogen-dipped towel strip. The nal apparatus is detached and reserved. It is possible to store this solution in the freezer; however, because benzene freezes at 5 8C, be aware that there is a risk of rupturing a break-seal. We have had success at storing the reagent at room temperature for many months. A polymerization must be accomplished to establish the concentration of DLI. An additive is advised to be used as a coinitiator with the use of this reagent to break up the aggregations, promote the solubility, and encourage a faster initiation event. We generally have good success with the use of lithium sec-butoxide (sec-BuOLi). sec-BuOLi Synthesis sec-BuOLi, used as an effective coinitiator, is synthesized from the alcohol by its reaction with Li metal according to this chemical reaction: sec-BuOH Li !sec-BuOLi 1=2H2 The preparation of the synthesis requires ampulization of sec-BuOH and purication of benzene. sec-BuOH is dried over salt (e.g., MgSO4) on the vacuum line with stirring overnight, degassed, and ampulized; subsequently, this ampule is attached to the synthetic apparatus. Benzene is chosen as the solvent because the prod-

Figure 39. tion.

Filtration of the product sec-BuLi solu-

III. Hexane is in-distilled to the apparatus, and the apparatus is again degassed. IV. The apparatus is sealed and detached from the vacuum line. V. The contents are thawed. The solution of BuLi is used to wash the entire inner surface of the apparatus and is then collected back to the purge recovery ask. VI. The apparatus is carefully rinsed by being allowed to reux from the purge recovery ask for at least 2 h. VII. Hexane is distilled to the reactor ask. It is not necessary to collect a large amount because it is desired to precipitate the product from this solution. (Keep in mind that the reagents are already ampulized in hexane as well.) For example, even at a $2-g scale of PEB, a reaction volume of $50 mL hexanes is plenty. A small quantity is easily collected to the downward appendages from the reactor. The purge recovery section is detached from the apparatus. VIII. The apparatus is inverted; hexanes are collected to the reactor ask (see Fig. 41). The reactor is set to stir at room temperature. IX. The seals to the ampules of PEB and sec-BuLi are ruptured, and their contents are rinsed into the reactor ask. The ampules may be detached. X. The reactor is shielded from the light by being wrapped loosely in foil. The reaction is left to progress for 3 days. Both PEB and sec-BuLi are soluble; the DLI

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6205

Figure 40.

Vacuum synthetic apparatus for the synthesis of DLI.

uct is not appreciably soluble in hexane; it may be left on the vacuum line in a puried reservoir. This synthesis is very similar to that of sec-BuLi; the apparatus needed is thus similar, except for the geometric provision that sec-BuOH must be poured into the reactor and not distilled. A portion of the vacuum synthetic apparatus required, showing mainly the geometric distinction from the previous ones, is depicted in Figure 45. The essential differences of this synthesis in contrast to that of sec-BuLi are as follows:  Benzene is used as the solvent instead of hexane, so that the product remains soluble.  sec-BuOH is allowed to enter the reactor by gravity.

 The reaction is exothermic, so the addition is made slowly with the reactor chilled in an ice bath, but the product is stable; hence the reactor may be allowed to warm to room temperature or even higher.  A blue color of products is visible.  The reaction is allowed to progress for $2 days.  Because H2 gas is evolved, the vacuum decreases; it is not mandatory to remove the gas because it will not interfere with an anionic polymerization, but if the reaction were to be carried out on a large scale, it would be perhaps wise to make a provision for this removal by the addition of an extra break-seal to the apparatus.

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Figure 41. occurs.

Reactor ask in which the chemical reaction between PEB and sec-BuLi

POLYMERIZATION PROCEDURES IN NONPOLAR SOLVENTS

Simple Technique1,2 The kinetics of polymerization in hydrocarbon media are very slow, and this means that the order of incorporation of reagents into the solvent is not necessarily crucial. A simple polymerization apparatus is shown in Figure 46. A simple stepwise procedure is given next. I. The apparatus is assembled, docked to the vacuum line, evacuated, veried for integrity by use of the Tesla coil, and ame-dried. The apparatus is degassed until a high vacuum is achieved. II. The solvent (e.g., benzene or cyclohexane) is in-distilled through the vacuum manifold from a puried reservoir. The apparatus is frozen with liquid nitrogen and degassed. The apparatus is sealed and detached from the vacuum line at the constriction. III. The solvent is thawed and allowed to warm to room temperature. The seals to the reagents are ruptured. The monomer (and additive) is added rst and is followed by the initiator. We accomplish the mixing of the contents by simply tumbling the apparatus, rinsing the ampules well, and collecting all contents back to the main ask. Stirring is generally unnecessary. IV. Afterward, the active polymer is deactivated by rupturing the seal to the methanol.

When breaking seals, be aware of vapor pressures on both sides. A highly volatile material (e.g., isoprene or even diluted butadiene) should be chilled before the seal is broken to avoid blowing the breaker too forcefully and risking shattering it. It is also wise to avoid letting

Figure 42. Removal of hexane and excess reagents from the product DLI.

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6207

polystyrene samples with controlled MWs in the range of millions. Purging is accomplished by using the procedure given here. I. The apparatus is assembled, docked to the vacuum line, evacuated, veried for integrity by use of the Tesla coil, and ame-dried. The apparatus is degassed until a high vacuum is achieved. II. BuLi is injected into the purge ask, the side arm is rinsed and sealed, and the apparatus is degassed. III. The solvent is in-distilled through the vacuum manifold from a puried reservoir. The solvent is frozen with liquid nitrogen, and the apparatus is degassed. The apparatus is sealed and detached from the vacuum line at the constriction.
Figure 43. ask. In-distillation of benzene to the reactor

IV. The contents are thawed. The solution of BuLi is used to wash the entire inner glass surface, by careful tumbling of the apparatus, and is then collected back to the purge recovery ask. V. The apparatus is rinsed. By gently warming the solution in the purging recovery ask, the solvent is condensed throughout the reactor. This solvent collects in the reactor ask and is poured back into the purge

breakers fall on the wrong end because they are weaker from that side; again, the risk is shattering the breaker. Sometimes even the glass walls of the reactor can be shattered. The mixing of monomers with solvent is usually exothermic, so mix these reagents carefully to avoid sudden uctuations in vapor pressure. The polymerization is left to proceed until all monomer is consumed ($68 half-lives; this can be 1 or more days, depending on the concentration and targeted MW). Linear block copolymers are obtained by the sequential addition of monomers: each monomer is polymerized before the addition of the next. The purity of the second (or later) monomer must be very high because any impurity will result in the premature termination of active polymer chains and, hence, a homopolymer contaminant in the nal polymer product. Purge Technique2 Generally purging is required when the targeted MW is high (>100 kg/mol) because there will be fewer moles of initiator used and, hence, a lower tolerance for traces of impurities. It is also necessary to employ this technique in the provision of lower MW materials if precision is required in the designed MW of the product. The drawing in Figure 47 illustrates how a simple polymerization may be easily modied to permit the purging of the reactor. For example, by using such an apparatus in the 1970s, Fetters23 was able to produce

Figure 44. Product DLI solution collected to nal split-down apparatus.

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Figure 45. Vacuum synthetic apparatus for the synthesis of sec-BuOLi: a partial depiction.

recovery ask by careful tilting of the apparatus. Repeating this periodically for a period of $2 h allows the collection of all BuLi, along with its reaction products with the impurities on the surface of the glass (which are also nonvolatile), back to the recovery ask. VI. The solvent is gently distilled from the purge recovery ask (20 8C) to the polymerization reactor ask (0 8C). Finally, the purge ask is detached from the apparatus by the sealing of the constriction. VII. At this point, the polymerization is set to commence upon the rupture of the break-seals. The procedure to be followed from this point onward is the same as that described for the simple technique. During the rinsing of the polymerization reactor and the nal distillation of the solvent to the reactor, it is very important to prevent the BuLi solution bumping from the purge ask into the polymerization reactor. Bumping is avoided more easily with a lower temperature differential as the motive of distillation. Avoiding the use of overly lled asks is also helpful (i.e., it is best to plan that the reactor be not more than half full).

Delayed Ampulization A monomer may, in some cases, be ampulized immediately before its use. There are two frequent situations that call for this technique: (1) the monomer is dangerously volatile at room temperature, or (2) the monomer is unstable upon purication. Figure 48 illustrates how an empty freeze ampule may be tted directly to a polymerization reactor. The overall procedure is thus a combination of the earlier given accounts of polymerization and freeze ampulization, appropriately timed. I. The polymerization is prepared up to the point of the need of the monomer, at which point the apparatus exists as shown in Figure 48. The apparatus is then redocked to the vacuum, and the empty ampule is used to collect the needed monomer by using the appropriate ampulization technique for the selected monomer. II. The monomer is taken by sealing the constriction, whereupon it is immediately incorporated into the polymerization. The delayed monomer may be collected to a reactor waiting for polymerization to commence, or it may be added to a polymerization already in progress (e.g., preparation of a diblock).

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6209

Figure 46.

Simple polymerization apparatus.

This technique is a useful way to avoid requiring the dilution of overly volatile monomers such as butadiene. It is also a good way to retain a high purity of unstable monomers because they are incorporated at once into the reactor, diluted, and placed into the scene of their desirable consumption. Canadian Technique in Detail3,24,25 An alternative geometry of an all-glass apparatus, which permits purging, is shown in Figure 49. This apparatus was developed and highly rened by the Canadian school of anionic polymerization, during the 1960s and 1970s, an elegant culmination of contributions from Worsfold, Bywater, and Roovers, among others. The technique remains timeless and lends itself easily toward new chemistries as they are explored. A detailed stepby-step account of manipulations is given here and is supported pictorially by Figures 4954. I. The apparatus in Figure 49 is assembled, docked to the vacuum line, evacuated, veried for integrity by use

of the Tesla coil, and ame-dried. The apparatus is degassed until a high vacuum is achieved.

II. BuLi is injected into the purge ask, the side arm is rinsed and sealed, and the apparatus is degassed. III. The solvent is in-distilled through the vacuum manifold from a puried reservoir. The solvent is frozen with liquid nitrogen, and the apparatus is degassed. The apparatus is sealed and detached from the vacuum line at the constriction. IV. The contents are thawed. The solution of BuLi is used to wash the entire inner glass surface by careful tumbling of the apparatus and is then collected back to the purge recovery ask. V. The apparatus is rinsed. By the apparatus being stood upright in a warm water bath, the solvent is allowed to reux from the purge recovery ask to the reactor (see Fig. 50).

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Figure 47. Polymerization apparatus adapted to a purge technique.

VI. The rinsing is continued for 2 h. The solvent may be collected to the remote appendages (by means of a towel strip dipped in liquid nitrogen, see Fig. 51). The apparatus may need to be periodically tilted, and the recovery ask briey chilled in a 0 8C bath, to facilitate the intermittent collection of all solvent back to the recovery ask from remote pooling locations within the reactor. (By careful construction, gravity will accomplish most of the solvent return. However, the downwardly pointing attachments must be raised above the horizontal to drain.) VII. The solvent is collected to the reactor in a gentle distillation procedure, as shown in Figure 52. VIII. The purge section is detached from the polymerization apparatus. The remaining polymerization apparatus is shown in Figure 53. IX. The polymerization is commenced.

Note that the collection ask is tted with a constricted break-seal exit; the solution may be mixed with another reactor, and the entire mixed contents may be

The basic Canadian apparatus is easily adapted. For example, with an apparatus such as the one shown in Figure 54, a polymerization from DLI is accomplished.26 The monomer, the initiator, and the coinitiator are all attached to the same arm. After the polymerization, an estimated amount of solution is collected into the sampling arm, where it may be detached and then quenched with methanol. Finally, a carefully calculated quantity is ampulized in the collection ask.

Figure 48.

Delayed ampulization technique.

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6211

Figure 49.

Canadian polymerization apparatus.

back-collected to the same ask and reampulized to await nal linking chemistry. THF may be nally added and the linking progress may be monitored by use of the small sampling ampules.

POLYMERIZATION PROCEDURES IN THF

Simple Technique The anionic polymerization of vinylic monomers in THF is a much more sensitive procedure than their polymerization in hydrocarbon media. THF is an active solvent, and the kinetics of the polymerization are much faster. The reactor must be briskly and continuously stirred. Polymerizations are generally accomplished within minutes instead of hours. The

advantage of using THF is that it is a more versatile solvent. Hence, a larger variety of monomers may be polymerized in this solvent. Keep in mind that in the polymerization of dienes, the microstructure obtained is very sensitive to the media. (The so often desirable, rubbery, cis-1,4 microstructure is obtained only through polymerization in hydrocarbon media with Li counterion.) A basic all-glass apparatus suitable for polymerizations in THF is shown in Figure 55. A modest step-bystep account of its use follows presently. I. The apparatus is assembled, docked to the vacuum line, evacuated, veried for integrity by use of the Tesla coil, and ame-dried. The apparatus is degassed until a high vacuum is achieved.

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IV. Monomers are sequentially incorporated into the reactor; each is allowed a brief period to polymerize before the seal to the next one is ruptured. V. The polymerization is quenched by rupturing of the seal to the methanol. The apparatus is allowed to warm to room temperature. During the polymerization, the external alcohol bath should be set to bathe the apparatus at a level beneath the level of the solvent inside the reactor. Otherwise, as monomers are incorporated, it is easy for them to accumulate and polymerize on the glass above the level of the solution, and an inhomogeneous system results. The initiator used is n-BuLi rather than sec-BuLi. sec-BuLi may react with THF somewhat more rapidly than n-BuLi, even at 78 8C. The active polymer chains may also be terminated if the reactor is allowed to warm during the polymerization. It is consequently difcult to take preliminary aliquots of the polymerization between additions of successive monomers. Monomers may not be poured into the reactor without being diluted rst in THF. If they are diluted and poured, they must be well chilled before the rupturing of break-seals. Alternatively, the monomers may be distilled to control the polymerization better. Distillation is recommended for the addition of all monomers after the rst one because the reactor is

Figure 50.

Rinsing of the apparatus.

II. The apparatus is closed from the vacuum. The seal to n-BuLi is ruptured, and the initiator is rinsed into the reactor with the hexanes. III. The reactor is set to bathe at 78 8C in a dry ice/ isopropyl alcohol bath. THF is distilled into the reactor from a puried reservoir on the vacuum manifold. The apparatus is sealed and detached from the vacuum line at the constriction.

Figure 51. Remote rinsing of the apparatus.

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6213

Figure 52. Distillation of the solvent from the purge attachment to the polymerization reactor.

not purged: distillation is the cleanest method of monomer transport. When using the distillation technique, it is wise to begin the distillation with the monomer cold and then allow it to gently warm, after the break-seal is ruptured, to avoid bumping the monomer into the reactor. In the synthesis of block copolymers, the reactivity of each monomer must be considered in determining the polymerization sequence. That is, in anionic polymerization, the resulting anionic chain end of each sequential

polymerization must be reactive enough to quickly initiate the polymerization of the next monomer. Consider the following reactivity scale:27 Styrenes % Dienes > Vinylpyridines > Methacrylates > Siloxanes % Oxiranes In other words, the anionic polymerization of each monomer in the scale leads to a macroanion reactive enough to initiate a polymerization of any monomer to its right.

Figure 53.

Canadian polymerization apparatus: nal apparatus.

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Figure 54. Canadian polymerization apparatus: complex apparatus example.

Polymerization of (Meth)acrylates It will be understood by now that the subtle variance among more elaborate glass apparatuses becomes as rich as the synthesists skill and imagination permit. The apparatus shown in Figure 56 is an example of such, as developed by Cook.28 The polymerization procedure is very similar to that described for the previous simpler apparatus; therefore, a new step-by-step account is not provided here.

An effective organolithium for the initiation of (meth)acrylates is diphenylalkyllithium. This initiator is generated in situ through the interaction of a stoichiometric quantity of n-BuLi with excess DPE. Of course, there is no inherent drawback in the earlier preparation of this organolithium. However, this delayed approach offers greater exibility in the synthesis of diblocks. More reactive monomers (e.g., styrenic compounds) may be polymerized rst from n-BuLi; the resultant

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6215

Figure 55.

Simple polymerization apparatus for use with the solvent THF.

macroanions are then end-capped with DPE before the cross-initiation of (meth)acrylate. The glass nger entry to the reactor helps to deliver the monomer directly into the vortex of the stirring THF solution. The glass path may be gently warmed with the hand torch before such distillations to dissuade monomers from stopping there and clogging the path. After using the torch in warming the glass, allow the reactor to become tepid before rupturing the seal to the monomer ampule. Additives may generally be omitted in the polymerization of methyl methacrylate. More reactive methacrylates and acrylates are often better controlled during polymerization through the addition of LiCl or LiClO4 to dissuade side reactions. Such compounds are completely nonvolatile and should be attached as closely to the reactor as possible. Purge Technique A reactor to be used for polymerization in THF is less frequently purged than one used for polymerizations in hydrocarbon media because of increasing difculty. However, this procedure may be accomplished. The purging agent used is diphenylhexyllithium because this organolithium is less reactive toward THF solvent, and the procedure is accomplished at room temperature (without greatly warming the purge ask to effect distilling or reuxing of THF). We can very

easily prepare this reagent as a stock solution by adding DPE to a bottle of n-BuLi and keeping it for multiple procedures. The glass apparatus shown in Figure 57 is useful for this experiment, illustrating a geometry that we have learned from Pitsikalis.3 After the injection of the purging agent, THF is in-distilled, and the apparatus is sealed. The apparatus is washed and rinsed by gentle distillation of the THF from the purge ask to the rest of the apparatus and its recollection back to the purge recovery ask several times. Because diphenylhexyllithium is attended by a deep red hue, it is easy to discern when the apparatus has been sufciently rinsed. THF is carefully distilled to the polymerization reactor and chilled, and the purge section is detached. Because the purging procedure requires a frequent tumbling of the apparatus, it is rather difcult to keep unstable monomers continuously cold. A delayed ampulization technique may therefore be necessary. The apparatus in Figure 57 shows this specic provision for one of its ampules.

LINKING MANIPULATIONS USING CHLOROSILANES: HELLENIC TECHNIQUE IN DETAIL3

The group of Hadjichristidis, Iatrou, Pispas, and Pitsikalis has developed and rened careful linking techniques

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Figure 56. Polymerization apparatus useful for the polymerization of (meth)acrylates in THF.

and exploited a modular linking chemical strategy, offering a strong synthetic methodology toward a wide variety of well-dened miktoarm (mixed arm; i.e., heteroarm) materials, as well as more complex graft materials such as ps and multigrafts.26,2933 This linking strategy is likely to remain another timeless example of a synthesists art over both glass and chemistry. The basic Hellenic linking apparatus is shown in Figure 58. The reactor is designed so that each manipulation is conducted through its own break-seal entry or exit to the reactor. In some cases, a clean delivery of polymer solution into the reactor is enhanced by the use of an inwardly protruding ngertip extension of the entry directly into the main reactor ask (illustrated more clearly in the following sketches). Intermediate sampling is permitted by means of small ampules attached to the reactor; thus, linking progress may be monitored by size exclusion chromatography (SEC). In the scene of Figure 58, a typical reactor is shown at the beginning of its use. The reactor is purged with a benzene solution of BuLi and rinsed, absolutely, for at least 4 h or better for 2 days while other work is done.

Finally, a small amount of benzene is collected to the linking reactor (in the appendages), and the purge recovery ask is detached. The linking reactor is at this point ready to be sealed toward the ampulized products of controlled anionic polymerizations through further glassblowing. Various manipulations each require a specic further assembly. These all-glass assemblies are further described in the following subsections and illustrated through the use of Figures 5962 and 64. Assembly of the Reactor to Flasks of Collected Active Polymer29 After the linking apparatus is prepared, the chlorosilane compound is introduced into the reactor. The empty ampule may be detached for a less clumsy apparatus. Each active polymer ampule is attached to the linking reactor through the assembly of an all-glass bridge (see Fig. 59 to visualize this construction). A double breaker (a breaker with a heavy collection of glass at both ends) is used. This assembly is carefully docked to the vacuum

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6217

Figure 57. Polymerization apparatus useful for THF polymerizations requiring a purge technique.

port (always use two persons for this step) and gently supported under each ask. The bridge is vacuumed for at least 1 h or until a high vacuum is attained. The assembly is taken by the sealing of the constriction. It is urged that this be done only with two persons: two hands are not enough. The assembly is then transported to a safe location. It is urged again that the apparatus always be well supported under both asks because their weight, especially if full, may introduce a lot of stress on the glass bridge and the break-seals between the two asks. The assembly is thus prepared for commencement of the linking event. The manner in which this manipulation is conducted is crucial to the success of the procedure and is described presently. End-Capping the Active Polymer with Excess Chlorosilane34,35 For the end-capping step to be successful, two things are important. First, the amount of silane used should be a great excess over the amount of active polymer chains; if it is possible, use a 100-fold excess. Second, the solution of active polymer must be added to the silane in one motion, without the silane being permitted to migrate (simple chlorosilanes are more volatile than benzene) into the ask of active polymer.

The second criterion is actually not difcult to achieve. Keeping the linking reactor cooler than the ask of active polymer, along with gravity, pulls the solution rather easily into the linking reactor. The linking reactor may be set to stir briskly in a pan of water; ice is added to the pan; and 30 s later (because benzene freezes at 5 8C, the reactor cannot be left at 0 8C for a long time), the seals are ruptured, and the assembly is tilted steeply, with a hand kept on the ask of active polymer for both warmth and support. Additionally, a towel soaked in warm water may be cloaked briey around the ask of active polymer for a few seconds to raise its vapor pressure. The addition event is pictured in Figure 60. The solution is thus added in one continuous increment to the linking reactor with brisk stirring throughout. After the addition has taken place, the assembly may be allowed to lie at at room temperature. The incorporation of the rst equivalent of active polymer chain into a chlorosilane is generally accomplished within several minutes, although we usually wait hours. As colored anions are adducted into Si, a visual indication is that their color completely dissipates. If the solution is concentrated, a light precipitation of LiCl may be noticed; this is inconsequential to the linking progress and indeed is evidence of the success.

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Figure 58. Hellenic linking apparatus.

Removing Excess Chlorosilane34,35 Excess volatile chlorosilane is removed after the endcapping procedure by means of the high-vacuum line. The reactor is assembled to the vacuum manifold through one of the break-seal entries. It is possible to use complementary ground glass joints and high-vacuum grease; however, because of the long experimental duration and sensitivity of the procedure, this is discouraged.

The better technique is to assemble the reactor directly to the vacuum manifold through an all-glass path (see Fig. 61 to visualize this assembly). Depending on the glassblowing style, two persons may be required for the assembly. The most important result is that there must be no stress on the glass bridge. Therefore, after roughly attaching the apparatus, clamp the linking reactor securely; if the reactor is large, two perpendicularly oriented clamps are better. The nal glassblowing is then

Figure 59.

All-glass assembly of the linking reactor to a ask of active polymer.

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6219

Figure 60. Addition of a solution to the linking reactor.

completed and the connection is annealed for several minutes with the hand torch, with a soft blue-yellow ame. Neither the clamps nor the apparatus is adjusted after this point.

Elsewhere docked to the vacuum manifold are a reservoir of puried benzene and a large waste collection ask, which are both well degassed. The stopcock to the linking reactor is opened, and the glass path is pumped until a high vacuum is achieved. The seal to the reactor is broken, and the contents are out-distilled to the waste collection ask until the solution becomes too viscous to stir. Freshly puried benzene is in-distilled to the reactor to make a $10 w/v % solution, and the contents are stirred to mix them well. The contents are again out-distilled. This procedure is repeated for a total of three out-distillations. After the third out-distillation, all of the solvent is carefully stripped from the polymer; the stopcock is carefully adjusted to avoid letting the polymer climb out the reactor. During the in-distillations, it is extremely dangerous to freeze the linking reactor with either dry ice or liquid nitrogen. Often the thick polymer syrup is strongly adhered to the glass, or the system freezes in an inhomogeneous manner. (Two different layers of the substance freeze: one is the concentrated polymer solution, and the other is the incoming solvent.) The result is that a lot of stress is placed on the ask; often mechanical failure cannot be prevented, and the glass cracks. It is strongly recommended to simply use ice water to chill the reactor, gently, while both the reservoir and the reactor are stirred. After the majority of solvent has been stripped from the polymer and it appears to become drier, the reactor may be opened directly to the main vacuum manifold. The main liquid-nitrogen trap must be cleaned after the rst day. It is important to ll the main liquid-nitrogen

Figure 61.

All-glass assembly of the reactor directly to the high-vacuum line.

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Figure 62.

Titration of a solution into the linking reactor.

trap vigilantly (twice per day). The reactor is pumped for 1 week under a high vacuum. The reactor may be left at room temperature. Optionally, the reactor may be gently warmed to 35 8C for a slightly faster evacuation. After 1 week, puried benzene is once more in-distilled to the linking reactor from the puried reservoir. The linking reactor is detached from the vacuum line, with two persons, by sealing the constriction. The polymer is left to dissolve overnight. An aliquot of the solution should be taken and compared with the sample of the quenched polymer before the end capping. SEC eluograms, before and after the end-capping procedure, should coincide and lack evidence of dimerization of the macroanions.

Titration of the Active Polymer into Stoichiometric Chlorosilane29,30 High-vacuum titration is an elegant procedure in which active polymer is added from a collection ask to the linking reactor incrementally. After each addition is made, a small quantity (several drops are sufcient) is removed from the linking reactor to monitor the linking progress with SEC. The discriminatory powers of chlorosilane electrophilic centers toward incoming macromolecular nucleophiles, based on their steric demands, is exploited fully. Because it is much more difcult to add a third arm of polystyrene to Si than it is to add a second one, it is

Figure 63. SEC eluogram composition (see the text for an explanation).

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Figure 64.

Final all-glass encapsulation to permit long-term linking completion.

possible to titrate the second equivalent of PSLi cleanly. Similarly, PILi may be titrated as a third equivalent. It is important that the aggregation behavior of the macroorganolithiums be controlled for a highly successful result. Alkoxides, which do not affect the course of a polymerization, may inuence the linking behavior. THF is a powerful additive and generally results in a marked enhancement of linking behavior and is, in most cases, avoided in titration procedures. Figure 62 depicts a titration in progress, for which a Hellenic linking reactor has been assembled to a ask of PSLi. By the careful raising and lowering of the ask of active polymer, dropwise additions of the solution to the linking reactor are controlled. Because PSLi is evidenced by a vivid orange-red hue, the progress of linking may be visually monitored in a qualitative way. SEC is the more important inspection, however, and eyes should never be relied on alone. Moreover, the relative height of each of the peaks in the SEC eluogram will give a quantitative impression of the progress of the titration, from which the size of the next future increment may be decided. The SEC composition shown in Figure 63 is exemplary: a titration of PSLi upon SiCl4 is illustrated in a waterfall plot. Here SEC eluograms of successive aliquots taken during the titration procedure are normalized with respect to the maximum peak height and are stacked toward the viewer sequentially. The rst aliquot (backmost eluogram) indicates a mixture of 25% (PS)2SiCl2 dimer and 75% PSSiCl3 unimer by mass. At the point of the second aliquot, the amount of the dimer has increased to 60%. Repeated small additions of PSLi to the reactor are attended by a steady decrease in the unimer content to less than 5%, whereas the high-MW

shoulders of the later eluograms show no evidence of the formation of (PS)3SiCl trimer. The titration is stopped when it is judged that there is no further progress in the shift of the SEC prole. Usually there remains a small quantity of unlinked material in the reactor. Often there will be a visual cue that the solution in the linking reactor remains more colored. Occasionally there will be evidence of overtitration (a small and unwanted high-MW shoulder grows), at which point the titration should generally be stopped. Final Linking Manipulations We make nal linking manipulations by collecting solutions of macromolecular electrophiles and nucleophiles together in a certain stoichiometry, sealing them in a convenient storage ask, and waiting for the linking to occur (see Fig. 64 to visualize a nal assembly of macromolecular reagents). Notice that the nal collection ask is equipped with a constricted break-seal exit. After the solutions are mixed, they are collected back into this new ask and reampulized. The nal macromolecular organolithium is often endcapped with several units of butadiene to relieve steric barriers. It is generally used in excess over the remaining Si Cl bonds ($1.2 equiv). The nal linking reaction is usually permitted several weeks. A small amount of THF may be added ($0.5 v/v %); this breaks up the aggregations and expedites linking events. Often 1 week in the presence of THF is sufcient for all linking to progress. The nal linking is monitored by the removal of small aliquots and their analysis with SEC. When no fur-

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ther shift toward a higher MW is discerned according to the SEC prole, the linking is judged to be complete.

CONCLUSIONS
In this compilation, we have attempted to collect and provide thorough, easy-to-follow, step-by-step instructions for performing the key manipulations that are required to accomplish syntheses of complex macromolecules through controlled anionic polymerization under high-vacuum conditions in all-glass reactors. We have placed special emphasis on technique, instilling an appreciation of the requirements of a vacuum system and the behavior of compounds within it, and also on safety because of the hazardous nature of certain manipulations. We sincerely hope that this work will be useful to workers in this eld, especially to novices as they seek to master these highly specialized techniques.
The authors acknowledge current sponsorship by the Division of Materials Sciences and Engineering, Ofce of Basic Energy Sciences, U.S. Department of Energy, under contract DE-AC05-00OR22725 with Oak Ridge National Laboratory, which is managed and operated by UT-Battelle, LLC. D. Uhrig is supported by an appointment to the Oak Ridge National Laboratory Postdoctoral Research Associate Program, which is administrated jointly by the Oak Ridge Institute for Science and Education and Oak Ridge National Laboratory. The authors are grateful to the referees for their many excellent criticisms and suggestions for improving this article. The authors are also grateful to the editors for bringing the work to fruition. J. W. Mays thanks Lew Fetters, Cheong Kow, and Barry Hostetter for introducing him to the joys of high-vacuum anionic polymerization. D. Uhrig thanks Marinos Pitsikalis, Yiannis Poulos, and Kunlun Hong: Real living polymers.

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