Production of Fluorescent

Backbone Molecule
CME 430-01 Group 13
Bradley Siefker, RJ Schratz, David Devlin, Trevor Langton
1/27/2017
Motivation
The Devlin, Schratz, Siefker, and Langton Fluorescent Chemicals (DSSLFC) has been
tasked to produce a metal free fluorescent backbone. Metal free fluorescent molecules may
promise increased effectiveness and use in medical imaging applications. Research has suggested
TPE may serve as a viable organic backbone for fluorescent molecules. Fluorescent signal
quenching may be less of an issue at higher concentrations than standard metal fluorescent
molecules [1]. The final TPE may be either used as a general fluorescent or modified to respond
to specific signals. The DSSFC is seeking to expand and develop a production facility capable of
producing 10,000 tons of tetraphenylethylene (TPE) per year to be used in organic fluorescent
applications.
Several concerns exist throughout the production of TPE, such as operator and
environmental safety, economic viability, and product safety. All reactants and intermediate
reagents in the production of TPE have the potential for large scale environmental destruction as
well as operator harm. All materials in the production of TPE will be treated as hazardous and
exposure to the chemicals will be limited using engineering controls and proper PPE.. Finally, to
ensure the fluorescent backbone molecule can be truly metal free, extra care will be taken to
ensure a 99.5% pure TPE compound with no trace metal remaining.

Literature Review
Product Market
Applications for TPE include Organic Light Emitting Diodes (OLEDs), photovoltaic
cells, and biological imaging via fluorescence. In each of these applications, a molecule produces
fluorescent light when electrons relax from an excited state. Other fluorescent particles on the
market cease illuminating when grouped tightly together, as their flat stereochemistry allows
them to stack on top of one another, limiting their absorption of light. [1] TPE, on the other hand,
does not exhibit this stacking as a result of its four phenyl groups [1], and thus does not
experience the quenching of luminescence that other compounds do when tightly packed
together. This trait makes the compound desirable in the manufacturing of OLEDs, as they are
produced as solids. Additionally, there are several means to adjust the color which TPE
derivatives emit, such as manipulating counter anions or molecule conformation.[2] Thus TPE
derivatives are not only a bright florescent in the solid state, but also a versatile one.
 TPE is also particularly useful as a biological indicator. The compound does not contain
harmful metals, unlike other fluorescents on the market, making it safe for medical use. [1] And
while TPE does not experience quenching when tightly packed together, there are conditions
under which TPE will not fluoresce. In these instances, electron excitement is dissipated
kinetically, as the molecule rotates about the double bond. [3] There are however, means to
reduce the rotational freedom of the bond, either by increasing steric crowding or by
manipulating the viscosity or polarity of its solvent. [3] This restriction causes the primary means
of energy emission to be light. This contrast in signal strength makes TPE an ideal candidate for
use in detecting tumors, where fluorescent indicators accumulate at the site. [1] On the other
hand, if constant luminescence is needed, other means of steric inhibition can be employed, such
as adding functional groups to the base molecule. Additionally, TPE can be attached to many
biological molecules, such as proteins and DNA, while still maintaining their fluorescent
properties. [1]
Lastly, TPEs ability to absorb and re-emit light also makes it useful in applications with
photovoltaic cells. Its anticipated use will be in Cadmium Telluride (CdTe) solar cells, which
will steadily increase in market share because of its reduced cost relative to crystalline silicon
cells.[4] CdTe cells do have one shortcoming, however, as they do not effectively convert light
with wavelengths under 500 nm to current.[4] To utilize a broader spectrum of light to generate
current, Luminescent Downshifting Layers (LDS) are deposited on the cells surface to absorb
these short wavelength photons, then re-emit the energy at a different wavelength which the cell
can convert to electrical energy.[4] In order for the luminescent layer to increase absorptive
efficiency of the cell, its absorption spectrum must have little overlap with that of the CdTe cell
to prevent energy losses. Thus, compounds used for LDS must exhibit large Stokes shifts.
Relative to traditional fluorophores, derivatives of TPE have larger Stokes shifts and thus reduce
the degree of parasitic absorption. [4] Additionally, this shift allows TPE derivatives to have a
greater degree of coincidence between its re-emission spectrum and the absorptive spectrum of
the solar cell. Lastly, these compounds exhibit thermal stability, making them viable for use in
this application. [4]
Production Method and Alternatives
DSSFC has access to the base reagent chemicals of chlorine gas (Cl2), phosphorous
trichloride (PCl3), and benzophenone to be used in the production of the TPE. Initial production
begins as chlorine gas is fed into a reaction vessel to produce solid phosphorus pentachloride
(PCl5) as shown in the reaction equation 1 [5] below.

3 + 2 5

The reaction takes place at room temperature under non-elevated pressure conditions. A
mixture of Cl2 vapor with an equimolar amount of liquid PCl3 is added to the reactor. A
continuous feed of each species is fed to the liquid and vapor reactor [5]. The liquid PCl3 is atomized
and interacts with the chlorine gas. The initial two species form the reactive solid intermediate
PCl5.
Transportation of the PCl5 to the second reactor is selected from analysis of
environmental and financial constraints. One potential mode of transport is for the PCl5 to be sent
to a sealed hopper where it can be safely transported with external methods such as a lift truck to
a feed location for the second reactor. Alternatively, the PCl5 may be fed directly into the second
reactor via a gravitational feed along with a feed of solid benzophenone. Gravitational feed is the
ideal transportation system to reduce the contact of operators with hazardous chemicals.
The secondary reaction in this sequence involves heating PCl5 and benzophenone in a
heated reactor. The reactor is heated at the base with cooling coils at the top to ensure any
evaporated material condenses and returns to the reaction vessel. This reaction vessel is held at a
temperature of 220oC to produce the second reactive intermediate diphenyldichloromethane
(DPCM) forms as shown in figure 1 below [6].

Figure 1: Chlorination of Benzophenone

An equimolar amount of Phosphorous oxychloride (POCl3) is also produced from this
reaction. The DPCM and POCl3 mixture is fed to a distillation column where the two products
are separated and the POCl3 byproduct can be cooled in a heat exchanger and sold as a
byproduct.
DPCM can also be produced in an alternate way using benzene, carbon tetrachloride, and
anhydrous aluminum chloride. A double Friedel-Krafts Alkylation of the benzene in the presence
of the excess chlorine will produce DPCM as shown in figure 2 [7].

Figure 2: Double Friedel-Krafts Aklylation of Benzene

A mixture of carbon tetrachloride and aluminum chloride is cooled to 5 to 10oC as
benzene is added [8]. Hydrogen chloride is released during this addition which makes the lower
temperatures necessary for safe handling. This method of DPCM production will require a
separation that exploits of the boiling point differences between benzene, carbon tetrachloride,
and DPCM. DPCM can be separated from a carbon tetrachloride and benzene mixture via
distillation, and aluminum will require an additional separation step.
There is little background experimental information on the alkylation of benzene rings,
and requires active cooling to prevent excessive heat release during reaction. The challenging
separation and exothermic reaction conditions make the demands of this separation unfavorable
compared to the use of benzophenone and PCl5.
After separation from the POCl3, DPCM is fed into a final reactor with a catalyst feed.
The DPCM can be converted to TPE by use of either nickel powder dissolved in glyme [9] or by
copper powder in dimethyl sulfoxide (DMSO) [10] as shown by the figure 3

Figure 3: Coupling of DPCM in formation of TPE

Nickel in glyme would serve as the ideal catalyst in this scenario as it is highly magnetic and
therefore a simpler separation route exists to ensure no metal contaminates the final products.
The catalytic reaction with the DPCM occurs at room temperature and yields >99% conversion
of DPCM into TPE in bench top reactions [9]. Filtering of DPCM and magnetic separation of the
nickel glyme complex yields a pure product of high purity solid TPE.

Safety and Environmental Concerns

Though the final product in this process, TPE, is not hazardous or toxic, reactants involved in the
production route selected by DSSFC are and require different precautions for handling to ensure
the safety of those involved [11]. In the chlorination of PCl3 both reactants can be potentially
dangerous. PCl3 can cause severe skin and eye damage and if swallowed or inhaled can be fatal
[12]. Exposure times of operators must be kept low to prevent damage to organs if inhaled. To
avoid these potential dangers, direct PCl3 exposure will take place in well-ventilated area, with
operators wearing gloves and a face shield [12].

Aquatic toxicity is also a concern. Over 1000 mg/L of PCl3 is the lethal concentration
after 96 hours for half of zebra fish (LC50) following exposure to PCl3 [12]. All material waste
from TPE production will be removed by an external disposal company where it will be
dissolved with a combustible solvent and burned in a chemical incinerator equipped with an
afterburner and scrubber [12].
PCl5 has similar properties to PCl3 so similar precautions and safety procedures should be
observed following the chlorination should any product be released [13]. Gloves, face shields,
and protective clothing should be worn to avoid any severe skin burns or eye damage. Like PCl3,
PCl5 is fatal if inhaled so the proper engineering controls listed are vital to ensuring employee
safety.
Chlorine gas arriving by rail car is pressurized and may act as an oxidizer in the presence
of combustible materials [14]. The incoming Cl2 shall be stored separate from any sources of
heat and ignition as well as other combustible materials to prevent ignition. In gaseous form skin,
eye, and respiratory irritation and possibly death could result from direct exposure. The LC50 for
rats exposed to Cl2 is 293 parts per million. Due to exposure concerns gloves and respiratory
protection are required for working with chlorine gas. Like the other components involved in the
chlorination step aquatic toxicity is a still a concern [14]. Air filtering will be a particularly
important environmental protection to ensure no Cl2 is released from the plant into the
atmosphere or into groundwater.
 The chlorination of benzophenone introduces another chemical with toxicities and safety
hazards particularly to humans. Benzophenone is carcinogenic, so any contact with the raw
chemical will not be permissible. The LD 50 of rats from dermal exposure was found to be 3535
mg/kg [15]. Benzophenone can form combustible dust so the areas where benzophenone is being
worked with will require adequate ventilation and recirculation to prevent both a fire hazard and
to remove the exposure risk to operators. Aquatic toxicity of benzophenone is extremely high as
well, with the LC 50 for fathead minnows being only 14.2 mg/L [15]. The combination of these
factors will ensure that benzophenone is exposed to atmospheric conditions as little as possible.
Engineering controls improving ventilation will be used to limit worker exposure to
benzophenone. Similar safety precautions to the previous reactants should be followed including
protective lab attire like gloves, face shields, respiration and protective clothing are mandated for
anyone in contact with benzophenone.
The reactive intermediate DPCM, similar to benzophenone, can form a combustible
material. At room temperature DPCM is liquid, but care must be taken to ensure no release of
vapor. DPCM vapors are denser than air, which may spread across the floor. The vapors of
DPCM have been known to react violently when contacting air during intense heating. DPCM
can also react violently with water, so all DPCM vapors will be contained for safe operation [16].
A condenser reflux will be designed into the reactor to prevent vapor release from the reactor.
Any employees working with or around DPCM during production process shall conduct work in
properly ventilated areas with the same personal protective equipment as working with the
benzophenone.
During the DPCM production, an equimolar amount of POCl3 is produced. The primary
concerns in working with POCl3 are toxicity concerns. The LC 50 in testing with rats was
determined to be 32 ppm [17]. As in working with DPCM and benzophenone adequate
ventilation will be required for all employees working with POCl3. In addition to the engineering
controls use of face shields, gloves, respirators, and chemical protection suits will be required for
all personnel working with POCl3.
Future Work
DSSLFC will address further considerations within the design process including
development of a process flow sheet, and the design of various reaction vessels and separation
systems. These items will undergo preliminary sizing, and concerns with material compatibility
will be addressed. Utility demands will be approximated from preliminary mass balances of the
production line. Labor costs of both technicians and supervisors will be estimated. To a lesser
degree, design of buildings and structures, piping, instrumentation and insulation will be
considered. Using the aggregate of these costs and constraints, DSSLFC will seek to determine a
price at which the production of 10,000 tons of TPE will yield a discounted cash flow rate of
return of 15%.

Design Alternatives
A limited number of viable synthesis routes exist for production of
diphenyldichloromethane (DPCM) from readily available chemicals. Two important designs
decisions must be made in order to ensure production of a safe high quality product.
Production of a DPCM intermediate is necessary in order to produce the final TPE
product. One means to synthesize this intermediate is double Friedel-Krafts alkylation of
benzene in the temperature range of 5 and 10oC in the presence of carbon tetrachloride and
anhydrous aluminum chloride as a catalyst [7]. Benzene, carbon tetrachloride, and DPCM are
separated by volatility differences. Excess aluminum chloride remains behind as a solid powder
which must be filtered to ensure no metal contaminates the final product. The boiling point of
DPCM at standard atmospheric conditions is roughly 305oC [16], much greater than the boiling
point of benzene (80oC) [18] and carbon tetrachloride (76oC) [19] allowing for easy removal of
DPCM. Benzene and carbon tetrachloride would not require additional separation following
removal of DPCM as they are not desired product. However, this production method would
require substantial energy usage in the heat exchanger network and separation system.
To avoid these additional utility costs, another production method, a reaction of
phosphorus pentachloride (PCl5) and benzophenone at 220oC [6] will be used. When the effluent
is cooled to room temperature, unreacted reagents solidify and can be filtered out to leave a
mixture of DPCM and POCl3 behind, with reduced risk of metal contamination relative to
production via the alkylation of benzene. Intermediates formed from this step can be separated
using volatility differences. Concerns associated with performing reactions with carcinogenic
benzene are mitigated when using the selected synthesis path.
The second design decision is the catalyst used in the production of tetraphenylethylene
(TPE) from DPCM. Two metal catalysts, nickel powder in glyme [9] and copper powder in
dimethyl sulfoxide (DMSO) [10], are viable for synthesis of TPE. Both catalytic reactions take
place at room temperatures and provide DPCM conversions of greater than 95%. A final
filtration separation will remove TPE from the liquid catalyst and unreacted liquid DPCM in
both catalyst paths. The primary consideration in this step is ease of removal of metal powders
from the catalyst. DSSFCs TPE is marketed as a nonmetal fluorescent chemical, thus removing
these catalysts from the product is vital. In order to ease removal of the metal powder the nickel
in glyme catalyst will be used in DSSFCs production of TPE. Nickel is a highly magnetic metal,
making magnetic separation feasible.
Two important design decisions that can reduce the operating cost and improve product
safety of TPE, are the intermediate and catalyst to use in the TPE production. The production
route of the reactive DPCM intermediate with benzophenone and PCl5 allows for a less energy
intensive separation system than with production via benzene. For TPE production, the Nickel
glyme complex as the catalyst will allow for an easier separation downstream from the product.
Nickel can more effectively be removed than less magnetic copper drastically reducing the risk
of metal contamination in the final product. These design decisions are based on the
thermodynamic and material properties of the reactants, intermediates, and products.

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