Hazard Evaluation of Polymerizable Compounds

D. J. Frurip, A. Chakrabarti, T. C. Hofelich, S. J. Martinez, and L. F. Whiting

The Dow Chemical Co., Analytical Sciences, Thermal Analysis 1897C, Midland, MI 48667

Reactive monomers are a special class of materials used widely in the chemical industry in the production of polymers. Many of these materials are thermally unstable and may polymerize during handling and storage with a release of significant amounts of energy. If this energy is not controlledproperly, it can lead to a runaway reaction. Compounding the concern for the stability of monomers is the fact that these materials are typically transported and stored in laqge volume. The undesired initiation of the polymerization reaction may be caused by a number of factors, including contamination, exposure to extreme enuironmental conditions, or inhibitor loss. For example, an unintended polymerization can result @oma seemingly benign procedure such as spill control with common absorbents. These and other factors mean that the reactive chemicals evaluation of monomers presents special problems and concerns which require more detailed experimental design for reliable hazard testing. This paper discusses the practical aspects of reactive chemicals testing strategies for monomers and rules-of thumb for monomer inhibition, compatibility, spill control, and so-called quenching (also called short-stopping) agents. The techniques discussed range from simple age and observe type tests to more sophisticated heat Jlux calorimetry evaluations. We also discuss the more routine application of Differential Scanning Calorimetry and Accelerating Rate Calorimetry to monomers. Vent sizing applications with the VSP device are also presented with emphasis on total containment during a runaway.

INTRODUCTION
The general term for the chemical precursor to a polymer is monomer. These substances are generated and used at large volume in the world chemical market. In many ways these substances present unique safety challenges to those faced with the production, storage, transportation, and ultimate processing of these commercially important materials. Most monomers are thermally unstable and, under the right conditions, may polymerize during handling and storage with the release of significant amounts of energy leading to a

runaway reaction. For most olefins, the heat of polymerization is on the order of -20 kcal/mol. The release of this quantity of energy, under adiabatic conditions, may result in temperature rises of 300-700C along with the potential pressure rise. Compounding the concern for the stability of monomers is the fact that these materials are typically transported and stored in large volumes. Monomers of course, are designed to be reactive but the key to their safe handling is controlling when and at what rate the materials react. The undesired (also referred to as unscheduled or unintended? initiation of the polymerization

Process Safety Progress (Voi. 14, NO. 2)

April, 1995

79

reaction may be caused by a number of factors, including contamination, exposure to extreme environmental conditions, or inhibitor loss. For example, an unintended polymerization can result from a seemingly benign procedure such as spill control with common absorbents. These and other factors mean that the reactive chemicals evaluation of monomers presents special problems and concerns which require more detailed experimental design for accurate, meaningful, and scalable hazard testing. This paper discusses the practical aspects of reactive chemicals testing strategies for monomers and rules-of-thumb for monomer inhibition, compatibility, spill control, and so-called quenching (also called short-stopping) agents. The techniques discussed range from simple age and observe type tests to more sophisticated heat flux calorimetry evaluations. We also discuss the more routine application of Differential Scanning Calorimetry and Accelerating Rate Calorimetry to monomers. Vent sizing applications with the VSP device are also presented with emphasis on total containment during a runaway. Although most of the discussion below concentrates on vinyl monomers, the same testing strategies and concerns should be applicable to other thermally unstable monomers which polymerize by mechanisms other than free radical. Numerous reactive chemicals incidents involving monomers have been documented in the open literature involving a wide array of materials [ I ] . Styrene has been involved in a number of unscheduled polymerization incidents [ 2 ] . In an incident involving acrylic acid, a runaway polymerization in a tank truck caused an explosion rupturing of the tank [ 3 ] .A large quantity of acrylic acid was involved in a well documented but poorly understood shipboard incident [ 41. A wealth of important information involving the stability of acrylic acid may be found in the numerous publications of Levy [5a-5b). In Brethericks Handbook of Reactive Chemical Hazards [6] there are no fewer than 70 incidents documented involving monomers. General engineering aspects of reactor design, operation, and emergency relief are discussed in reference [ 7 ] . Reference [ 8 ] is an excellent review of the literature with regard to violent polymerization incidents involving industrially important monomers. Potentially the best source for hazard information and specific handling guidelines for a specific monomer is the manufacturer. In reality, however, the degree to which a supplier is forthcoming with (or for that matter knowledgeable of) specific, accurate, and useful information for hazardous monomers varies widely from company to company. This suggests that nothing should replace in-house testing of the materials using those testing protocols which experience has shown to yield reliable results. As described below, the level of knowledge required for safe handling of monomers depends on many factors such as scale, storage conditions, etc. This paper describes some of the testing protocol we find useful at the Dow Chemical Company.

0 1 2

3 4

5 6 7 8 9 1011121314

r i In wwks (e68-n.~)
FIGURE 1. TBC depletion rate in styrene [91 for various initial levels of TBC. Data such as these are invaluable for determining maximum storage time for monomers.

GENERAL ASPECTS OF MONOMER INHIBITION/ATMOSPHERE REQUIREMENTS

Most commercial vinyl monomers contain inhibitors (at the ppm level) which are typically antioxidents. Many styreneics are inhibited with TBC (t-butylatechol) and most acrylates are inhibited with MEHQ (methylether of hydroquinone). In most cases, dissolved oxygen is required for the inhibitor to be active. Although the exact mechanism for this synergistic relationship is not perfectly understood for all monomers, it probably proceeds by rapid reaction of a spontaneously generated monomer radical with oxygen to form a peroxide radical which is relatively long lived. This peroxyl radical then reacts with an inhibitor molecule to form non-radical products and thereby effectively stops the chain reaction. Thus, it is critical to understand and comply with the atmo-

spheric requirements of a monomer in order to insure storage stability. The inhibitors used to stabilize monomers are eventually depleted during storage and thus, it is also important to understand the kinetics of disappearance of the inhibitor. For most commercially used monomers the depletion rate is quite slow and typical shelf lives are on the order of months at ambient temperature. For example, the rate of disappearance of TBC in styrene is shown in Figure 1 [ 9 ] .Oxygen is also depleted by the inhibition process and may need to be replenished. Sometimes the manufacturers recommend a continuous sparge of air through the monomer. If flammability in the headspace is a concern, a sparge of reduced oxygen in N, may be better. Unfortunately, only the large commercial-volume monomer systems (styrene, acrylic acid, etc.) have been studied in detail as to the inhibitor depletion rate and oxygen requirements. For many specialty monomers the inhibition requirements are less well known. An important aspect of oxygen requirement for inhibition is the potential for peroxide formation. During ambient storage of a monomer with sufficient inhibitor, the dissolved oxygen acts to stop the propagation and acceleration of the free radical chain mechanism and is thus, beneficial to the safety of the process. If, however, the inhibitor level is insufficient (by normal depletion or removal by any mechanism), peroxide formation can become quite rapid (even autocatalytic) for Some monomers (styrene for example). At the early stages of peroxide formation, the system may remain stable, but the peroxides formed can acts as initiators and eventually can

80

April, 1995

Process Safety Progress (Vol. 14, No. 2)

for a monomer to be used safely, for this greatly depends on the scale and other factors. Testing protocol which may be employed to answer most of these questions is discussed in the remainder of this paper. 1. What is the monomer inhibited with (if at all) and at what recommended concentration? 2. How fast does the inhibitor get consumed during storage? 3. What is the minimum inhibitor level to be effective? 4. Are there atmospheric requirements to keep the inhibitor effective, e.g. is dissolved 0, required? Is air sparging recommended? 5. If dissolved oxygen is required, what is the minimum level to be effective? How fast does the oxygen get consumed during storage? 6. What testing has been performed to demonstrate the inhibitor effectiveness? 7. How is the monomer stability affected by contaminants (such as rust, heat transfer fluids, or pump fluids) and/or materials of construction? 8. Are there analytical procedures or simple Test Kits for determining the inhibitor level in the monomer? 9. In the event of an unscheduled polymerization, are there materials which can be added to the system to quench the reaction? If so, what is the best way of introducing and mixing the material in an emergency? 10. Does the monomer have a propensity for peroxide formation? Are the peroxides soluble in the monomer? What are the best ways of controlling peroxide formation? How is the stability of the monomer affected by the presence of peroxides? 11. If the monomer freezes, what hazards are associated with the thawing process (does the inhibitor fractionate?)? 12. Have the recommended absorbents been tested for compatibility with the monomer? 13. Does the monomer have a propensity for polymerization on the headspace walls of the storage vessel after condensation in the headspace? If so, are there procedures for periodic inspection of the emergency relief systems? 14. Have any waste streams which contain monomer been tested for their stability? Has any consideration been given to inhibition of such waste? 15. For mixed monomer (or monomer plus other) storage systems, has the compatibility of the mixture been tested? 16. If the monomer can come in contact with another immiscible phase (such as water), will the inhibitor partition into the new phase? (An example of this is TBC in styrene which can be depleted by water contact.) 17. During an adiabatic runaway polymerization of the monomer, will further exothermic processes take place which add to the hazard? (Acrylates, for example, can typically reach a temperature at which an exothermic, gassy decomposition reaction takes place). 18. Is the emergency relief device on the storage vessel sufficient?

Iowper~lurr, deq

(,sale

,IT

Xelvln,

FIGURE 2. Self heat rate versus temperaturetraces from Accelerating Rate Calorimetry (ARC) experiments on freshly distilled styrene containing various levels of styrene (po1y)peroxide. The peroxides were generated by bubbling pure oxygen through styrene at 40C and the sample was periodically analyzed electrochemically for the peroxide level. As the level of peroxide increases, the detected polymerization onset temperature decreases and the maximum observable rate during runaway increases dramatically. (The data are not corrected for bomb mass heat capacity; phi=1.5 for all runs; sample mass approx. 4.5 9.1

significantly destabilize the system. A good example of this is uninhibited styrene which is stable in air for short periods of time. Figure 2. shows a series of Accelerating Rate Calorimetry test results from our laboratory on styrene containing various levels of styrene peroxide, the latter being generated by bubbling pure oxygen through uninhibited styrene at 40C for several days. As can be seen, styrene is destabilized as the peroxide levels are increased as indicated by a lower detected onset temperature. Also, and perhaps more importantly from a hazard mitigation standpoint, the rates of heat generation at some temperatures are orders of magnitude larger with the peroxide initiated reaction. The lesson to be learned from the above discussion is that although a tank of monomer may appear stable (free flowing, clear, non-viscous), the potential for a significant hazard due to thermal runaway may exist. Monomer users should always consider some monitoring of both the headspace atmosphere and inhibitor level in stored material. 0ldermonomer might also be considered for peroxide level analysis and promptly used or disposed of if significant amounts of peroxides are found. Also, during a runaway, it may not be wise to consider air sparging of the system unless the inhibitor is added and mixed as well. Certain exceptions do exist, however, for the oxygen requirement. Notably, VDC (vinylidene chloride), vinyl acetate, and 1,3-butadiene are inhibited but it is recommended that these monomers be stored under oxygen free conditions. In some cases, peroxide formation (when oxygen is present) presents a serious hazard even in the presence of inhibitor [ l o ] .

THERMAL STABILITY STUDIES OF MONOMERS TYPICAL MONOMER QUESTIONS AND CONCERNS

Presented below, is a checklist of questions which may be considered when one is confronted with the task of evaluating the reactive hazards of monomers. These questions are ones which we have developed (or been asked to answer) over the years as a result of real life concerns in our companys operations. Not all the questions need to have answers

Testing Strategies for Monomers

Because of some of their unique properties, special consideration must be given to testing monomers for their reactive chemicals hazard potential as part of any hazard review. We have developed a number of testing strategies for accurately assessing the thermokinetic stability of monomers and have developed some useful rules-of-thumb. In general, we believe

Process Safety Progress (Vol. 14, No. 2)

April, 1995

81

that Differential Scanning Calorimetry is not a very effective tool for initial screening of many monomers. This is due to two limitations. First, because of the atmosphere requirements for most monomer storage, testing should be performed under controlled atmosphere conditions. This is typically difficult to do with DSC unless one adopts special sample encapsulation techniques such as sealed glass capillary/ampoule technology [ 11, l l a , 121. Second, and more importantly, the kinetics of polymerization of many monomers are dominated by low activation energy processes. This means that the detection of the exothermic polymerization process is more difficult than higher activation energy processes. Peak shapes in the DSC traces tend to be broad and thus, difficult to accurately interpret. The DSC detected onset temperature of an event may be considerably higher than more sensitive techniques such as ARC (Accelerating Rate Calorimetry) [13].This is mainly due to the fact that DSC is a scanning temperature technique and that it is relatively insensitive compared to other techniques [ 141. Complicating matters is the fact that the inhibitor may delay the detected onset considerably and thus, further increase the disparity between detected exothermic activity and the actual temperature at which the material is unstable. (As discussed below, this latter problem is not as great in the ARC.) What this means in practical terms is that DSC detected onset temperatures for low activation energy monomer polymerizations should not be used to determine temperature requirements for safe storage of these materials. It is important to note, however, that DSC testing can sometimes be used effectively to determine the efficacy of inhibitors as described below. In our laboratory, all monomers are screened via ARC testing using a variety of testing strategies which depend on a number of factors including the scale of the process and desired storage conditions. ARC is a sensitive technique which yields more meaningful data with which to make decisions regarding storage requirements. ARC tests also give valuable temperature rate and pressure data which, after applying appropriate scaling parameters, allow one to predict what would occur during an actual thermal runaway. Some monomers, acrylic acid and other acrylates are notable examples, can reach high enough temperature during runaway conditions to cause other decomposition processes to occur which can significantly add to the hazard potential 1151. The following is a list of typical experiments for monomers in order of (general) decreasing priority. This strategy may be modified depending on the amount and type of data provided by the manufacturer, and the quantities of monomer involved (a more extensive testing program would be necessary for larger amounts of monomer).
1. Standard ARC run of inhibited monomer under air atmosphere (typically tested 30 to 350C). (A standard ARC run in our laboratory includes a 5 degree heat step and a 15 minute wait time.) This initial screen yields general, yet accurate, information about the thermal stability of the material. 2. ARC, isothermal age of inhibited monomer at some worst case storage or transportation temperature (a hot day in Texas for example) for 24-48 hours, followed by a standard temperature ramp to 350C. This type of experiment can yield information about the adequacy of the inhibition under worst case conditions. The length of time to age the sample will depend on the actual scenario. 3. For those monomers which require dissolved oxygen to keep the inhibition process active, a standard ARC run of inhibited monomer with oxygen removed by sparging with nitrogen and then run under a nitrogen atmosphere. This type of run will elucidate the hazards associated with loss or depletion of dissolved oxygen during storage.

4. Standard ARC run of inhibited monomer mixed with

typical process contaminants. Many monomers are particularly sensitive to destabilization by contaminants such as rust. Careful review of the process should be made to determine the most likely contaminants which may include materials of construction (carbon steel fines for example), heat transfer fluids, pump seal fluids, metal oxides (rust), etc. 5. ARC test of the efficacy of short-stoppingyquench agents. This testing could yield important information about the ability of any material to stop a runaway polymerization. Details of this testing are discussed in a separate section of this paper. 6. Sensitive Heat-Flux Calorimetry testing of the monomer. Current commercially available calorimetric instrumentation allows a direct measurement of the heat liberated from a sample during actual storage conditions. These calorimeters are known as heat-flux calorimeters and can be as much as 100 times more sensitive than the ARC. Thus, one is able to accurately measure heat evolution from a sample under actual storage conditions (20-30C). The measured heat rates using this, more sensitive technique, can then be compared to a reasonable extrapolation from the ARC experiment.

Experimental Determination of Inhibitor Efficacy

Some of the key questions in the study of monomer inhibition relate to the efficacy of the added inhibitors and the kinetics of their disappearance under various temperature conditions. Clearly, one needs to know that an added inhibitor indeed acts to prevent polymerization and does not initiate the polymerization. We haue had more than one eaperience in which a commercially available inhibitor actually decreased the stability of the momomer! Once one is assured of the inhibition behavior of the additive, the next question relates to the length of time the material remains stable, i.e., the length of time required for the inhibitor to deplete to an unsafe level.

Inhibitor Efficacy
The ability of an additive to act as an inhibitor is relatively straightforward to test using DSC or, in some cases, ARC. Figure 3 shows a series of DSC traces illustrating this technique. In this series of experiments all the samples were sealed in glass capillaries. One DSC trace is of a peroxide initiated monomer mixture and detects the expected polymerization exotherm near 120C. When various candidate inhibitors are added to the sample the DSC traces now exhibit a delayed detected onset. The larger peak heights for the inhibited samples are due to the fact that once the inhibitor has reached a level in which it is no longer effective and the polymerization begins, the reaction rate is enhanced due to the higher temperature and the relatively large amount of unreacted monomer present. Care must be exercised in using the results of these tests to make decisions about ambient temperature inhibition efficacy due to a possible change in mechanism. ARC testing can be used in a similar manner as the DSC testing just described except that one has to be careful in interpreting the data. This is because the ARC testing, the effective temperature ramp rate is quite low (ca. O.l/min) compared to a typical DSC experiment (ca. IW/min) which may allow the inhibitor to burn out prior to the detected polymerization onset. Thus, in many cases, an ARC experiment on uninhibited monomer may appear identical to one which is inhibited. This is not true in all cases, however, and one may see a delayed detected polymerization onset in the ARC due to inhibition.

82

April, 1995

Process Safety Progress (Vol. 14, No. 2)

2,

WASTE MONOMERS
For various reasons, significant reactive chemicals problems can be associated with the handling of so-called waste monomer. These materials are typically the result of product stripping operations and in many cases are stored in relatively large quantities for either recycling back into the polymerization process or for eventual disposal. Due to the process by which the monomer is recovered, these materials may not contain any inhibitor, may be deoxygenated (the process may have operated under reduced pressure or under a nitrogen pad), and may contain any number of other process contaminants. All of these factors can contribute to a loss of temperature control during handling due to an unscheduled polymerization. For the above reasons, it is always beneficial to carefully review the way in which waste monomers are handled in a chemical process. Consideration should be given to the re-addition of inhibitor to the material. For materials which are recycled into the process, the choices of inhibitor may not be large since consideration has to be given to the effect such additives have on the product. At the very least, one should always test the thermal stability of the waste stream (using techniques described in this paper).

W P (C)

FIGURE 3. A series of DSC traces of a peroxide initiated vinyl monomer mixture (sealed in glass ampoules, scan rate 1OC/min). Polymerization of the uninhibited mixture is detected near 120C. Inhibited mixtures (curves A and B) exhibit delayed detected polymerization onset temperatures. The first peak is due to chemical initiation of the system, whereas the second peak is due to thermal initiation.

Inhibitor Depletion Rate

The determination of the rate of inhibitor consumption is more difficult experimentally but no less important. Classically, experiments have been developed to detect the volume changes in thc sample when polymerization begins [161. Unfortunately, most of these tests are designed to run at temperatures significantly higher than the actual processing or storage temperature and therefore are fraught with the problems of large extrapolation ambiguities. One has to be extremely careful in this process due to a possible change in mechanism, either polymerization o r inhibition. One testing strategy we have used is to isothermally age the sample in a calorimeter at a worst case storage temperature (4O0C-5OC for example). When the inhibition period ends, the measured heat rate should significantly increase due to the release of polymerization energy. The problem is that most of the calorimeters already discussed (DSC and ARC) may not be sensitive enough to detect this event. One could perform a series of experiments of this type at elevated temperaturcs ( i.e. at temperatures where the polymerization rates are high enough to be detected) and extrapolate via an Arrhenius typo plot (log of the induction time VS. 1/T) to ambient conditions but, as just discussed, there may be an unknown change in mechanism. The use of very sensitive heat-flux calorimeters can alleviate this problem. These instruments are much more sensitive than the A R C and are able to detect the desired heat effects under conditions closer to ambient. A direct (and unambiguous) way to determine the inhibitor depletion rate is by actual chemical analysis of both the inhibitor and the polymer level for samples aged under storage conditions. In this way the minimum inhibitor level can be determined accurately. This technique, whereas quite time consuming, generally expensive, and involved, can yield very useful and unambiguous data. We have, on occasion, performed even simpler tests for some monomer mixtures. This involves the aging of mixtures under ambient or slightly elevated temperature conditions and literally watching the samples visually for signs of polymerization (increased viscosity, the presence of solids, etc.). The presence o r absence of polymerization can often be detected by weighing any residue after evaporation (under vacuum if necessary) of the residual monomer. Process Safety Progress (Vol. 14, No. 2)

MONOMER-MONOMER COMPATIBILITY
In the processing of monomers it is sometimes convenient to mix various materials in storage tanks prior to addition to the polymerization reactor. Sometimes these mixtures are comprised of various mixed monomers (in addition to other non-monomer materials). We have found, using A R C testing, that certain monomer mixtures are inherently more thermally unstable than the pure materials. In ARC experiments the detected onset of polymerization is lower than either of the pure materials. This change in thermal stability as detected by the A R C testing may or may not represent a serious hazard and depends on the magnitude of the lowering of the detected onset temperature. It is, therefore, a good idea to test for the compatibility of mixed monomer systems and not to assume that the mixture is as stable as the lowest stability monomer in the mix.

SPILL CONTROL
A relatively common occurrence in chemical processing is the use of an inappropriate absorbent material for spill control of monomer containing streams. What typically happens in a plant situation is that an absorbent material is chosen for a spill based on convenience, i.e., it is the absorbent which is handiest. Unfortunately, many common absorbents are known to deactivate the inhibitors used in monomers, or even initiate the polymerization of monomers by either the heat evolved during the absorption process or by some chemical initiation. The problem is exacerbated by the fact that once a spill is controlled with the absorbent, the contaminated material is typically drummed. During the time awaiting disposal, they are prime candidates for thermal runaway (low thermal conductivity, relatively large volume, thermally unstable). We recommend that monomers should be tested for their compatibility with spill control absorbents prior to actual use. The testing protocol which we perform at Dow includes ARC and may also include heat of mixing calorimetry. The heat of mixing calorimetry allows one to estimate the maximum adiabatic temperature rise for the absorption process which can be compared to the detected onset from ARC experiments for the neat monomer. Also, ARC data for the monomer-absorbent combination can be compared to the A R C run on

April, 1995

83

FIGURE 4. Self heat rate versus temperature traces from Accelerating Rate Calorimetry (ARC) experiments on inhibited styrene and styrene in contact with a clay based absorbent. The styrendabsorbent experiment was an attempted isothermal age at 60C.

called expanded polymeric absorbents. These materials are made up of polypropylene (or polyethylene) and probably do not contain any potential active functional sites for initiation of the polymerization. The special problems concerning monomers and absorbents unfortunately continue to be ignored in the public and government literature. A recent compendium designed to help select appropriate absorbents for spill control never mentions the special problems of monomers and, in fact, classifies acrylic acid and acetic acid in the same category [It?]. When contacted about this problem, the authors remained unconvinced that this is a concern [19]. An example mentioned above of an incompatible mixture is styrene and clay based absorbents. An ARC self heat rate plot of styrene alone and styrene absorbed on clay absorbent is shown in Figure 4. One sees a significant lowering of the detected onset of polymerization with the absorbent/styrene mix. In general, if we see any change in the ARC self heat rate trace, we deem the absorbent to be incompatible. This might seem too conservative but we believe that the diversity of absorbents available makes it quite straightforward to chose a safe absorbent (from a reactivity standpoint) even based on this stringent criterion.

the pure monomer. In general, if there is a change in the detected onset temperature or if there is a change in the apparent activation energy with the monomer-absorbent combination, we recommend that alternative absorbents be considered. Some general guidelines have been developed at our company and some of this work has been published [ 1 7 ] . In general, any clay based absorbent or mineral based absorbent (vermiculite for example) are not good choices for all monomers. In the latter case we have found certain lots of mineral absorbents to be non-initiating while others were a problem. Styrene containing streams are particularly susceptible to initiation by these materials. We have also found that acrylic acid is best treated with sodium carbonate. During the treatment, the acid is neutralized (with only a slight release of heat) and excess carbonate then acts as an absorbent. Dilution of the acid with water, prior to the carbonate treatment, helps in reducing the hazard. Care must be exercised in this case to ensure adequate vent relief due to the CO, released. The most "benign" absorbents we have tested are the so-

QUENCHING STUDIES
A common question from those who deal with the handling of monomers is: "What can I add to stop or slow the polymerization if a temperature excursion is detected? This question is typically asked with regard to storage, or, actual polymerization of the sample in the reactor. There are two major considerations when deciding on an answer:
1. What inhibitor (also called a "short stopping" agent) has the free radical scavenging ability to bring the excursion back under control? 2. How can the agent be added to the polymerizing mass in such a way as to get it mixed properly and thus, be effective in the quench?

m
a
a
w

w
3
vi

L n

E 10'
L

9 8 7
G

f
KO 70
8C 90

i00

ii0 TEMP1

i20
"C

130 140 150 160 170

1
200

220

2 4 3 2 G C 28C 3 0 0 3 2 0 350 3 8 0 T E M P E R Q T U R E [ - l / T K S C A L E ) . "C

FIGURE 5. Pressure versus temperature during a runaway polymerizationof styrene using the VSP. The pressures were calculated using two Dow proprietary models for polymerization runaways. - VSP Data; * Calculation 1; --- Calculation 2.

. ---

FIGURE 6. Self heat rate versus temperature for a (premixed) hydrogen peroxide initiated polymerization of a monomer using VSP and ARC. The background heat rate for the VSP experiment was 0.5'Qmin. Note that the ARC detected the polymerization onset at a lower temperature than VSP. With 100 ppm Hydrogen Peroxide in the VSP --- Uninitiated Polymerization in the VSP; - With 100 ppm Hydrogen Peroxide in the ARC.

-----

84

April, 1995

Process Safety Progress (Vol. 14, No. 2)

The first question can be answered by various straightforward calorimetric tests which are discussed below. The second question is an engineering problem and is often the most difficult one to answer! Once the polymerization begins, the viscosity may increase to the point that any mixing strategy may fail. Of course perfect mixing is often not necessary. Quenching of the reaction to a sufficient extent to maintain vessel integrity or to allow easy cleanout of the reactor (after the contents have cooled) is often all that is required. We have attempted to shot add the quenching agent to a polymerizing mass in an ARC sample container via syringe injection. This technique has, on occasion, been successful in stopping the polymerization. The problem is that when the injection is not successful, we are always faced with the question of whether or not the injected quenching agent was mixed properly in the sample container. We have decided that it is better to attempt to quench in a device which has better stirring capabilities such as the FIKE VSP (Vent Sizing Package) [ 20, 20al. Alternatively, one can premix the quenching agent into the sample prior to loading the sample container. As the sample is heated in the calorimeter, the free radical scavenger behaves as though, in effect. it were instantaneously injected into the sample as the material begins to polymerize. Any delay in the detected onset temperature indicates that the added reagent has some ability to inhibit the polymerization. An example of this type of testing is shown in Figure 3 (discussed earlier) which shows a series of DSC traces of a particular styrene based monomer mixture initiated with a peroxide chemical initiator.

SUMMARY AND CONCLUSIONS

We have shown that a number of factors must be considered when addressing the thermokinetic stability of monomers. Special and careful consideration must be given to the design of reactive chemicals tests in order for the results of those tests to be meaningful and to ensure the safe handling and storage of these commercially important materials.

ACKNOWLEDGMENTS
The authors would like to thank the following people for assistance with and guidance for many of the monomer stability projects which formed the background to this paper: J. Bruce Powers, Robert Thomas, Robert Reim, Robert Zondlak, Leroy Swim, Sergio Cutie, Ziad Iskandarani, Steven Humphrey, Steven Sandor, Gene Dickens, A1 Taylor, Den0 OConnor, Jim Roe, Deb Diedering, and David Ortman.

LITERATURE CITED
1. Bond, J., Loss Preu. Bull., 65, p. 26 (1985). 2. Harmon, M., et al., A Review of Violent Monomer Polymerization, Rept., AD-017443, Richmond, VA, USNTIS (1974). 3. Anon., RoSPA OS&H Bull., 10, p. 3 (1976). 4. Kurland, J., et al., Plant/Operations Progress, 6, p. 203 (1987). 5. Levy, L . B., J. Poly. Sci., 23, p. 1505 (1985). 5a. Levy, L . B., Plant/OperationsProgress, 6(4), p. 188 (1987). . B., Plant/OperationsProgress, 8(2), p. 105 (1989). 5b. Levy, L 5c. Levy, L . B., J. Appl. Poly. Sci., 45, p. 1537(1992). . B., J . Appl. Poly. Sci., Part A, 30, p. 569 (1992). 5d. Levy, L 5e. Levy, L . B., Process Safety Progress, 12(2), p. 111 (1993). 5f. Levy, L. B., Process Safety Progress, 12(1), p. 47 (1993). 6. Bretherick, L., Handbook of Reactive Chemicals Hazards, 4th Ed., Butterworths (1990). 7. Encylop. Polym. Sci. Eng., 14, pp. 805-827 (1988). 8. Case Histories of Accidents in the Chemical Industry, Washington, MCA, SD-37 (1971). 9. The Dow Family of Styrenic Monomers, Form 11500608-1289, The Dow Chemical, Midland, MI 48640. 10. Bretherick, L., Handbook of Reactive Chemicals Hazards, 4th Ed., Butterworths (1990). 11. Whiting, L. F., M. S. LaBean, and S. S. Eadie, Thermochim. Acta, 136, p. 231 (1988). l l a . Thou, J. C., and L. F. Whiting, Thermochim. Acta, 42, p. 21 (1980). 12. Batch, G. L., and C. W. Macosko, Proc. North Am. Them. Anal. SOC., I. R. Harrison, Ed., 1, p. 474 (1989). 13. Accelerating Rate Calorimeter (ARC) Instruction Manual, Columbia Scientific Instruments, Austin, Texas, CSI-008/6/90. 14. Hofelich, T. C., and R. C. Thomas, Proc. Int. Symp. Runaway Reactions, AIChE, p. 174 (1989). 15. Whiting, L. F., and J. C. Thou, J. Thermal. Anal., 24, p. 111 (1982). 16. Boundy, R. H., and R. H. Boyer, Styrene, Its Polymers, Copolymers and Derivatives, ACS Monograph Series, Reinhold (1952). 17. Hankin, S., J . Hazard Mad., 13, p. 217 (1986).
April, 1995
85

EMERGENCY RELIEF TESTING FOR MONOMERS

Our (Dow) most common method for sizing emergency relief for monomer systems is the VSP. Practically all the monomer systems are sized for an external fire scenario. The advantage of using the VSP is that it requires minimum knowledge of the kinetics and the physical properties for the process. This becomes particularly important when the reactions are complex, or the VSP temperature rate trace has several (overlapping) exotherms. The relatively large volume of sample in the VSP, the safety of the high pressure containment vessel, the low phi factor, or better agitation via an impeller allows the use of the VSP in certain special cases. One of the special cases uses the maximum measured pressure to design reactors to contain a runaway reaction. Because of environmental considerations, this approach is becoming more important. Figure 5 shows an example of the pressure generated during a runaway polymerization (external fire scenario). Two separate internally developed software packages reproduced the measured rate of temperature rise very well. However, as seen in Figure 5, the calculated pressures are significantly different than the measured ones. This difference may be related to the use of interaction parameters measured at significantly lower temperatures, or potential non-equilibrium in the actual systems. Simulation of the addition of small amounts of contaminants, or catalysts, or short-stops are easier in the VSP, because the added amount is larger by a factor of 20, and/or the agitation is better. Figure 6 shows an example where the addition of a 100 ppm of hydrogen peroxide to a monomer was simulated. The rates of temperature rise from the uninitated reaction and the initiated reaction in the VSP, and the initiated reaction in the ARC are shown in Figure 6. Even after considering the 1ostparts of the exotherm in the ARC (during heat-wait-search), it was found that more than 75% of the hydrogen peroxide decomposed before initiating the polymerization. (Passivation procedures were the same in the

VSP and the ARC.)

Process Safety Progress (Vol. 14, No. 2)

18. Melvoid, R. W., S. C. Gibson, and R. Scarberry, Sorbents for Liquid Hazardous Substance Cleanup and Control, Noyes Data Corp., ISSN 0090-516x (1988). 19. Gibson, S. C., Asea Brown Boveri Environmental Services, personal communication (letter, 1991). 20. Fauske, H. K., and J. C. b u n g , G e m . Eng. Prog., 81(8), p. 10 (1985).

20a. Fauske, H. K., and H. G. Fisher, Thennochim. Acru, 104, p. 13 (1986).

This paper (9e) was presented at the AlChE Spring National Meeting in Atlanta, Georgia on April 18, 1994.

86

April, 1995

Process Safety Progress (Vol. 14, No. 2)