Analysis of 3D printing possibilities for the development of practical applications in synthetic organic chemistry

Article abstract of DOI:10.1007/s11172-016-1492-y

The possibility of rapid manufacturing of customized chemical labware and reactionware by three-dimensional (3D) printing is discussed. The advantages and disadvantages of this approach to the design of chemical equipment from different engineering plasti

Full text of DOI:10.1007/s11172-016-1492-y

Russian Chemical Bulletin, International Edition, Vol. 65, No. 6, pp. 1637—1643, June, 2016
1637
Analysis of 3D printing possibilities for the development
of practical applications in synthetic organic chemistry
E. G. Gordeev, E. S. Degtyareva, and V. P. Ananikov
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Eꢀmail: val@ioc.ac.ru
The possibility of rapid manufacturing of customized chemical labware and reactionware
by threeꢀdimensional (3D) printing is discussed. The advantages and disadvantages of this
approach to the design of chemical equipment from different engineering plastics were demonꢀ
strated and the suitability of some materials for chemical applications was estimated: PP > PLA >
> ABS > PETG (PP is polypropylene, PLA is polylactide, ABS is acrylonitrile butadiene
styrene, and PETG is polyethylene terephthalate glycol). The procedure described is a powerꢀ
ful tool for the production of both typical and unique chemical labware; to date, the fused
deposition modeling (FDM) method is already available for the everyday use in chemical
laboratories. The examples of successful application of 3Dꢀprinted products were demonstratꢀ
ed: solvent resistance and impermeability were assessed, as well as Pd(OAc)2ꢀcatalyzed crossꢀ
coupling between pꢀbromotoluene and phenylboronic acid and Ni(acac)2ꢀcatalyzed hydroꢀ
thiolation of alkyne with thiophenol were performed.
Key words: 3D printing, FDM method, labware, crossꢀcoupling, hydrothiolation.
Key features of chemical studies are a wide variety of
reagents, products, and types of chemical reactions. A great
number of chemical transformations has been discovered
in the field of organic synthesis,1,2 photochemistry,3 catalꢀ
ysis,4 materials science,5 and biotechnology.6 It is no wonꢀ
der that chemical sciences need a great variety of labware
to carry out chemical reactions. Many chemical processes
require unique labware and equipment whose production
from glass or metal by classical methods can be complex
and expensive.
The manufacture, cleaning, reuse, and storage of glassꢀ
ware and laboratory equipment are often the most reꢀ
sourceꢀ and timeꢀconsuming steps of a chemical study.
The emergence of a versatile technology for rapid producꢀ
tion of labware can change dramatically the current situaꢀ
tion.7 Since the advent of threeꢀdimensional (3D) printꢀ
ing, forecasts on revolutionary changes in practical impleꢀ
mentation of chemical experiments have been being made.
The methodology of 3D printing assumes manufacturꢀ
ing of a product based on its threeꢀdimensional model.
Modern computer aided design systems possess necessary
possibilities for the design of threeꢀdimensional objects.
Therefore, 3D printing minimizes the distance between
a project and its realization. Having designed a threeꢀdiꢀ
mensional model of a future product, one can start its
automated manufacture with a selected material.
sis. On the one hand, 3D printing allows production of
singleꢀtype labware, such as test tubes, flasks, beakers,
cuvettes, etc. About one hundred and more (depending on
the size) such products can be produced in one workday.
On the other hand, 3D printing allows one to considerably
accelerate and make cheaper the production of a complex
chemical reactors with unique construction whose manuꢀ
facture by other methods is either very complex or unreaꢀ
sonably expensive. Thus, chemists cease to be restricted in
their work only with commercial labware and can create
its by themselves customizing the labware to the features
of certain experiment.8
Many researchers wonder whether 3D printing will inꢀ
deed introduce a new dimension into laboratory chemical
applications.
In the present work, the most common and available
3D printing process, Fused Deposition Modeling (FDM),
was tested for practical chemical studies. Virtually
any thermoplastic polymer is suitable for this process and,
to date, a relatively wide range of inexpensive materiꢀ
als are available, which allows one to select a materiꢀ
al being the most suitable for certain chemical task.
In addition, FDM 3D printers have a simple design, are
easyꢀtoꢀhandle and the cheapest devices for 3D printꢀ
ing. We tested the most widely used plastics for FDM
printing: PLA (polylactide), ABS (acrylonitrile butadiene
styrene), PETG (polyethylene terephthalate glycol), and
PP (polypropylene).
Application of a singleꢀuse labware (no cleaning and
storage) will simplify and make cheaper chemical syntheꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1637—1643, June, 2016.
1066ꢀ5285/16/6506ꢀ1637 © 2016 Springer Science+Business Media, Inc.

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Gordeev et al.
The most important reactions for the carbon—carbon
and carbon—heteroatom bond formation, in particular,
the Suzuki—Miyaura crossꢀcoupling catalyzed by palladiꢀ
um acetate Pd(OAc)2 and alkyne hydrothiolation cataꢀ
lyzed by nickel acetylacetonate (Ni(acac)2), were perꢀ
formed in an FDM plastic labware. These chemical transꢀ
formations are a powerfool tool for the preparation of comꢀ
plex organic substances with atomic precision.1,2
stability of plastics under the synthesis conditions and to
perform chemical reactions, we chose the test tubes as the
most widespread, simple, and convenient type of labware
used in the vast majority of chemical laboratories (see
Fig. 2). To produce test tubes by FDM, four different
materials were used: ABS, PETG, PLA, and PP (see Fig. 2).
Crossꢀcoupling and hydrothiolation were performed in test
tubes with screw caps which were equipped with a septum
for better tightness (see Fig. 2, b, c).
Results and Discussion
To evaluate the suitability of 3Dꢀprinted labware, three
types of tests were performed: a) evaluation of chemical
resistance to solvents; b) pressure and vacuum leak tests;
and c) stability in chemical reactions.
Chemical resistance of the FDMꢀprinted labware. The
present work shows the effect of chemical solvents under
conditions of a chemical experiment on the labware proꢀ
duced by the FDM process. For this purpose, screwꢀ
capped test tubes made of ABS, PLA, PP, and PETG
plastics were printed (see Fig. 2).
The test tubes were filled with solvents which were
stirred for 1 h at ∼20 or 50 °C. The solvent was then transꢀ
ferred into a flask and evaporated. The flask was weighed;
the weight gain showed the amount of the plastic materiꢀ
al extracted by a solvent. The intensity of solvent interacꢀ
tion with a platic material serves as a suitability index of
the material for chemical experiments in different media
(Table 1).
The data given in Table 1 suggest that, in this series,
there is no universal thermoplastic material which would
be stable in all solvents. At ∼20 °C, ABS test tubes were
dissolved in the most of organic solvents (acetone, MeCN,
CH2Cl2, and THF) and, at 50 °C, the test tube walls became
3D printing technology. Threeꢀdimensional printing is
based on the additive principle. In the FDM printing proꢀ
cess, a material as a thin filament (with a typical diameter
of 1.75 or 3.00 mm) reeled on a spool is fed into an extrudꢀ
er, where it is heated to specified temperature. A thermoꢀ
plastic polymer passes into a viscousꢀflow state and is exꢀ
truded from a nozzle as a thin wire. The extruder is moved
over a platform where a model is built layerꢀbyꢀlayer. In
such a way, we created a typical chemical labware (Figs 1
and 2) to carry out this work. The layer height defines to
a some degree the spatial printing resolution: the lower is
the layer height, the smaller are the parts that can be
reproduced in a printed product. For example, even a relaꢀ
tively high layer height (0.2 mm) allows creating a large
operable thread to screw on tube caps and to provide a test
tube with tightness during the experiment (see Fig. 2, b, c).
Thus, our experiment showed that 3D printing is
a simple and convenient method for application in the
everyday practice of a chemical laboratory. The next aim
of our work was to study whether the FDMꢀcreated labꢀ
ware is suitable for chemical experiment. To test the
Fig. 1. Examples of typically used labware produced by FDM 3D printing with PLA: Erlenmeyer flask, roundꢀbottom flask, funnel,
test tubes, and beaker.
Note. Figures 1 and 2 are available in full color on the web page of the journal (http://www.link.springer.com).

3D printing for synthetic organic chemistry
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 6, June, 2016
1639
a
b
c
Fig. 2. Different types of test tubes used in the crossꢀcoupling experiments: short test tubes with threadless caps (a); 3Dꢀprinted thread
on the external side of a tube and inside a cap (b); and elongated screwꢀcapped tubes made of different materials (c).
softer in DMSO and toluene. Water, hexane, diethyl ether,
and ethanol do not dissolve plastic materials and, thereꢀ
fore, are considered as mild solvents: these solvents are
suitable for reactions in test tubes made of any tested maꢀ
terial (ABS, PETG, PLA, and PP).
PLA test tubes dissolved in dichloromethane and THF
and, during the experiment with acetonitrile at 50 °C, they lost
rigidity and broke down. At room temperature, this effect
was not so noticeable and test tubes did not lose their
physical properties; therefore, PLA labware can be applied
with MeCN without heating.
PETG test tubes dissolved only in dichloromethane and
THF; however, another problem emerged during the study:
the solvent permeated through the tube walls. This phenoꢀ
menon is due to a specificity of the FDM threeꢀdimenꢀ
sional printing process: PETG filaments upon printing
were stacked above each other in layers and, apparently,
do not stick together sufficiently to form a monolithic wall
under printing parameters recommended for this material.
As a result, the resulting product is porous and the solvent
flows out of micropores.
PP test tubes showed the best chemical resistance to tested
solvents. However, this material also has disadvantages,
such as shrinkage during printing and necessity for their
further mechanical processing to provide the accuracy in
size. After additional mechanical processing, products conꢀ
tain fine polypropylene particles adhering to the product
walls, which are sometimes difficult to remove completely.
Impermeability of the FDM labware. One of the most
important properties of any chemical equipment defining
Table 1. Solvent resitancea of plastic test tubes (50 °C, 1 h)
Solvent
ABS
PLA
PP PETG
b
Acetone
Acetonitrile (MeCN)
Water
–
–
+
b
c
–
+
+
+
+
+
+
+
c
c
+
+
–
Hexane
Dimethylsulfoxide (DMSO)
Dichloromethane (CH2Cl2)
Diethyl etherc
Tetrahydrofuran (THF)
Toluene
+
+
–
–
b
–
–
+
–
c
+
b
+
–
–
–
+
Ethanol (EtOH)
+
+
+
a The plastic material is not suitable for solvent experiments (–);
partially suitable: 2—7 mg of the plastic dissolved during the
experiment ( ); and chemically stable: the solvent has no effect
on the plastic (+).
b ∼20 °C, 1 h.
c The solvent partially permeates through the tube walls.

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Gordeev et al.
Table 2. Conversion of pꢀbromotoluene and
product yield in the Suzuki—Miyaura reacꢀ
tion (see Scheme 1)
its suitability for everyday chemical experiments is its leakꢀ
tightness. Therefore, the leakꢀtightness of printed test tubes
was studied under excessive pressure of 1 bar produced by
an air compressor and under reduced pressure of 30 mbar
produced by a rotary evaporator (to examine how test tubes
can keep vacuum during evaporation of a solvent). The
PETG labware were found to be nontight in both cases,
whereas the ABS, PLA, and PP products demonstrated
a high tightness in all experiments.
It was found that not only the material type and the
wall thickness of an product, but also its shape have effect
on the labware tightness. In particular, 50ꢀmL roundꢀbottom
polypropylene and PETG flasks were not leaktight in both
vacuum and excessive pressure experiments. The leakage
of flasks was first of all due to a high porosity of a material
near its spherical bottom and in the fixation region of the
flask neck, whereas, in the equatorial part of the flask, the
material is sufficiently impermeable.
Material
Conversion
Yield
%
Glass
ABS
PETG
PLA
PP
96
94
94
95
93
79
54
53
50
42
are partially transparent, while tubes made of other plasꢀ
tics are nontransparent. After the reaction was completed,
50 μL of the reaction mixture was sampled into an NMR
tube with CDCl3. The measured degree of conversion in
all cases was >90%, but the product yield was the highest
in glass test tubes (79%) and considerably exceeded the
value obtained in plastic test tubes (42—54%, Table 2). The
GCꢀMS study of the reaction mixture showed that, in
plastic test tubes, pꢀbromotoluene was almost absent in
solution, while triphenylboroxine was present in a considerꢀ
able amount. It is most likely that this is due to the sorpꢀ
tion activity of plastic materials towards pꢀbromotoluene,
which caused a decrease in the product yield. When planꢀ
ning experiments in plastic labware, this phenomenon
should be taken into account and its effect can be deꢀ
creased using the excess of sorbing agent. It should be
noted that the reaction mixture after completion of the
reaction in the PP test tube virtually did not contain pallaꢀ
dium particles: the catalyst was adsorbed on the tube walls.
The second model reaction was hydrothiolation of
alkynes10 with Ni(acac)2 as the catalyst (Scheme 2). This
reaction was performed in the medium being more aggresꢀ
sive towards plastic materials, toluene; therefore, ABS was
not suitable for this reaction: the reaction mass due to
partial dissolution of the plastic material was a thick and
sticky mixture and we failed to extract the reaction prodꢀ
uct with petroleum ether.
The reason for the leakage of all items is their layered
structure. To dispose of this disadvantage, the material
was fritted upon thermal postprocessing. However, heatꢀ
ing of roundꢀbottom polypropylene flasks at 200 °C reꢀ
sulted in an incomplete disappearance of microporosity
and the flask remained permeable.
Thus, the best tightness parameters were observed for
cylinderꢀshaped items made of ABS and PLA.
Chemical reactions in the FDM labware. At the next
step of this study, we applied the printed test tubes in
chemical synthesis. SuzukiꢀMiyaura crossꢀcoupling was
chosen as the model reaction (Scheme 1), since it proꢀ
ceeds under aerobic conditions in the waterꢀalcohol
medium and palladium nanoparticles act as the catalyst.
To obtain reliable data, this reaction should be carried out
in a labware containing no metal even in trace amounts,
for that reason the labware should be cleared thoroughly
after each exploitation or applied only ones,9 that became
possible upon introduction of the 3D printing technology
into a laboratory practice. The reaction was performed in
screwꢀcapped glass, ABS, PP, PETG, and PLA test tubes
(see Fig. 2, b, c).
Scheme 1
Scheme 2
i. Ni(acac)2 (2 mol.%), toluene, 40 °C, 3 h.
i. Pd(OAc)2 (2 mol.%), Et3N (2 equiv.), EtOH, 40 °C, 5 h.
An interesting result was obtained during the experiment
in a PLA test tube: the reaction mass contained an amorphous
coarse precipitate which was easy to remove by filtration;
that significantly facilitated the work up procedure.
The reaction was carried out under heating in a heat
block with a magnetic stirrer for 5 h. The visual control of
the reaction was complicated, since only PETG test tubes

3D printing for synthetic organic chemistry
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 6, June, 2016
1641
Table 3. Conversion of thiophenol and
product yield in hydrothiolation of alkynes
(see Scheme 2)
Table 4. Overall test of the suitability of FDM labware for
chemical experiments
Method of use
PP
PLA
ABS
PETG
Material
Conversion
Yield
Mild solventsa
+
+
+
–
+
+
+
–
+
+
Agressive solventsb
Pressure/vacuum
Chemical reactions
in mild solvents
–
–
+
%
Glass
ABS
PETG
PLA
PP
68
—*
71
82
82
47
—
27
37
44
+
+
Chemical reactions
in agressive solvents
General score
+
–
Good
Good
Satisꢀ
Satisꢀ
factory factory
* ABS dissolves in toluene.
a Mild solvents are Et2O, EtOH, hexane, and H2O.
b Agressive solvents are acetone, MeCN, CH2Cl2, THF, toluꢀ
ene, and DMSO.
The degrees of conversion for the reactions in test tubes
are also related to sorption of reagents by plastics (Table 3).
However, this effect was decreased due to the use of
twoꢀfold excess of thiophenol and the product yield, for
example, in the PP test tube, differed insignificantly from
that obtained in the glass tube.
PLA labware are characterized by better properties: they
have almost no pores and are tight, the material does not
shrink considerably and is convenient for additional meꢀ
chanical postprocessing. Although PETG items are parꢀ
tially transparent and this fact is their doubtless advantage;
the layered structure obtained upon printing hinders the
application of PETGꢀprinted labware due its high porosity.
The low chemical resistance of ABS considerably restricts
its applicability in chemistry. As a result, one can conꢀ
clude that PP and PLA are much more suitable for printꢀ
ing a labware compared to ABS or PETG. A general order
of the functionality of plastic materials for chemical apꢀ
plications is as follows: PP > PLA > ABS > PETG.
For further development, the following disadvantages
use of FDMꢀprinted labware should be noted:
• the plastic labware is not transparent, which makes
it difficult to control visually the course of the reaction;
• some items, in particular, PETG and PP ones, are
not tight and a solvent permeates through the material
layers;
• the data on the chemical stability of materials available
for 3D printing are limited; therefore, the effect of reagents
on materials should be checked prior to experiment;
• even if a material itself do not decompose on expoꢀ
sure to a chemical reagent, during the experiment one can
find that the reagent escapes from the reaction due to
a high sorption capacity of the plastic material;
* * *
Threeꢀdimensional printing technology can find a wide
application in chemical laboratory and become a versatile
tool for the design of not only standard labware (test tubes,
flasks), but also a more complex unique equipment. This
possibility allows solving unconventional problems which
earlier required high time and material costs. This work
was aimed at the study of the applicability of a labware
produced by fused deposition modeling (FDM) in order to
reveal possible operational difficulties and to take them
into account in the future. The test tubes used in the present
work are only a convenient "form" to test materials comꢀ
monly used for FDM 3D printing.
We showed that all plastic materials under study are
suitable for application in waterꢀalcohol media; therefore,
the 3D printing technology can find a wide application in
biology and medicine, especially, in the case when a sinꢀ
gleꢀuse smallꢀsize labware, such as arrays of cuvettes, vials,
weighing bottles, etc, is needed. In more aggressive media,
one should use materials with a high chemical resistance
(PP). In the case when a thermoplastic material was stable
under the reaction conditions, the data obtained were virtually
no different from those obtained in the glass. It should be
noted also that such materials as PLA and ABS are more
suitable for 3D printing, since the obtained model posꢀ
sesses a higher dimensional accuracy and integrity and
requires minimum mechanical postprocessing, whereas PP
shrinks considerably, which results in the difference beꢀ
tween the sizes of a printed product and its computer model.
As it follows from the overall assessment (Table 4),
polypropylene is the most suitable material for chemical
experiments due to the highest resistance to chemical reꢀ
agents; PLA possesses lower chemical resistance, however
• sometimes there emerge difficulties upon stirring the
reaction mixture, since even at insignificant softening of
the material, the magnetic stir bar sticks in the plastic and
stops to fulfil its function;
• the properties of a plastic material of the same type
can differ noticeably depending on the manufacturer;
therefore, in each case one should test the material in
several model experiments.
Beyond all doubt, a rapid development of the 3D printꢀ
ing technology occurring in the present time will provide

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Gordeev et al.
its considerable improvement and, in the nearest future,
one can expect an extensive use of a unique customized
labware made of not only plastics, but also of metal alloys
and even glass in chemical studies.11
This work was financially supported by the Russian
Science Foundation (Project No. 14ꢀ50ꢀ00126).
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PLA and ABS (ESUN), as well as PETG and PP (FLꢀ33)
were used as plastic materials.
3D Printing. All labware items were produced by fused depoꢀ
sition modeling (FDM) using a Picaso 3D Designer Pro 250
printer. The diameter of the starting plastic filament in all cases
was equal to 1.75 mm, the layer height (resolution along the Z
axis) was 0.2 mm, the extrusion multiplier was 0.9—1.0, the
printing speed was 45 mm s–1, and the infill was 100%.
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the table temperature (Tt) was 50 °C; during printing cooling was
performed using a fan installed on the printer extruder. For ABS,
Te = 230 °C and Tt = 100 °C. For PETG, Te = 210 °C and Tt = 50 °C.
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bubbles after switching on the compressor allowed to determine
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were connected to a rotary evaporator to produce a reduced
pressure of 20—30 mbar. The test tube was considered to
be leakꢀtight if the readings of a vacuum meter did not change
for 15 min.
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Crossꢀcoupling. 4ꢀBromotoluene (0.5 mmol, 0.086 g) was
added to a solution of phenylboronic acid (0.6 mmol, 0.073 g),
Et3N (1 mmol, 0.101 g), and Pd(OAc)2 (0.01 mmol, 0.002 g) in
EtOH (1 mL). The reaction was performed for 5 h at 40 °C. The
precipitate was separated by centrifugation and the organic phase
was collected using a Pasteur pipette. The precipitate was washed
additionally with ethanol (2×1.5 mL). The solvent was evaporated.
1
The product yield was calculated from the H NMR spectrum
using trimethyl(phenyl)silane as the internal standard.
Hydrothiolation. The reaction was performed according to
a known procedure13 using toluene as the solvent. A solution of
2ꢀmethylꢀ3ꢀbutynꢀ2ꢀol (1 mmol, 0.084 g) and Ni(acac)2
(0.02 mmol, 0.005 g) in toluene (0.4 mL) was cooled with stirꢀ
ring to 10 °C. Thiophenol (2 mmol, 0.220 g) was added and the
test tube was purged with argon and closed. The reaction was
performed at 40 °C for 3 h. The reaction mass was filtered through
zeolite to separate the catalyst and the unreacted starting reꢀ
agents were removed in vacuo.
7. M. D. Symes, P. J. Kitson, J. Yan, C. J. Richmond, G. J. T.
Cooper, R. W. Bowman, T. Vilbrandt, L. Cronin, Nat. Chem.,
2012, 4, 349.
The authors are grateful to F. A. Kucherov and S. S.
Zalesskiy for assistance in the leakage test of labware.

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12. RepetierꢀHost v. 1.5.6., 2011ꢀ2015, HotꢀWorld GmbH&Co.
KG, Willich, Germany, http://www.repetier.com.
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lics, 2006, 25, 1970.
Received February 8, 2016;
in revised form March 16, 2016