Institute of Chemistry Eötvös Loránd University

Effect of SnCl4 coinitiator concentration on

room temperature carbocationic
polymerization of β-pinene

Anik Virág
TTK AKI Polymer Chemistry research group

Supervisor:
Dr. Verebélyi Klára

2023.11.15.
Directions & goals of
polymer chemistry
Rubber wood & rubber milk

• Polymers have been a part of our everyday lives

…for a long time
• Initially made of natural materials (e.g. natural
rubber), nowadays synthetic polymers (the first
was Bakelite)
• Mainly petroleum-based polymers
• In recent decades there has been a growing
focus on renewable raw materials
• Renewable monomers for example terpenes of
plant origin
• Subject of my current work: β-pinene
Introduction of β-
pinene
• Member of terpene family
• Produced by distillation of turpentine from pine bark
and derived from wood chips
• By-product of paper industry  makes the
production economically advantageous
• Already used as an adhesive, medicine, rubber
additive etc.
• Currently AlCl3 Lewis acid coinitiator is used in its
industrial polymerization procedure

β-pinene
Theoretical
background
n
• Terpenes: hydrocarbons, contains one or more C-C
double bonds + consist of the same isoprene unit Poly(β-pinene)
• Poly(β-pinene)
• The reactive exo-position double bond enables the
carbocationic chain polimerization mechanism

R-X iniciator
LA Lewis acid
Nu nucleophilic additive

Verebélyi et al Int. J. Mol. Sci., 24, 5170

Theoretical
background Room temperature polymerization

• A lot of research tried to optimize the

polymerization and using wide range of
materials
• Lewis acids used, for example: AlCl3, AlBr3,
EtAlCl2
• Effective reactions mostly around - 80°C
• Recently appeared research about room
tempreture synthesis

Kukhta et al Green Chem., 13, 2362-2364, (2011)

Goals

1 2 3
Succesful carbocationic Investigation of the Determination of
polymerization of effect of SnCl4 Lewis monomer conversion,
β-pinene at room acid concentration on polymer molecular
temperature the polymerization weight distribution and
percentage of double
bonds / monomer units
Used materials &
methods
• Materials:
Benzotrifluoride
• β-pinene
• SnCl4
• Benzotrifluoride (BTF)
• Methanol
• Methods:
• GPC
• NMR
 114 mM SnCl4

Quantity n c
Material
Experimental part (cm3) (mol) (mol/dm3)

Benzotrifluoride 51.9

• Distillation of BTF and β-pinene (adventitious -pinene 7 0.0448 0.73

water will be an initiator)
SnCl4 0.8 0.0068 0.114
• Polymerization investigated at two SnCl4
concentrations
• Conditions: argon atmosphere, 25 °C (in 157 mM SnCl4
glovebox, with mixing and heptane bath)
• Total volume of reaction mixture: 60 cm3
Quantity n c
• Polymerization was started by addition of Material
SnCl4 to BTF and β-pinene (cm3) (mol) (mol/dm3)
• Sampling at 5, 30, 60 and 120 min (10 cm3) ,
injected into methanol Benzotrifluoride 51.9
• Purification of the polymers
-pinene 7 0.0448 0.73
• GPC and NMR measurements
SnCl4 1.1 0.0094 0.157
Results: Polymerization with
114 mM SnCl4 concentration

• 40 % conversion after 5 minutes

polymerization
• After sample 2, the conversion decrease may
have been caused by inadequate drying
• GPC chromatograms show monomodal,
symmetrical curves t Conversion Mn Mw Mp
D
• Relatively uniform polymer chain lengths (min) (%) (g/mol) (g/mol) (g/mol)
• At 60 and 120 min, shoulder appear 
inadequate purification/oligomer formation 5 40.2 2260 3950 3230 1.75

side reactions 30 47.1 2000 3650 3180 1.83

60 44.3 1750 3560 3210 2.03

120 46.9 1980 3070 2690 1.55

Results: Polymerization with
157 mM SnCl4 concentration

• Converson increases continuously

and reaches 56%
• GPC chromatograms show
monomodal, symmetrical curves
• Mn of the polymers varies between
1500-2000 g/mol Conversion Mn Mw Mp
t (min) D
• Relatively uniform polymer chain (%) (g/mol) (g/mol) (g/mol)
lengths
• Oligomer formation can be seen in 5 38.1 2110 3650 3140 1.73
the low molecular weight region 30 49.3 2080 3580 3020 1.72

60 51.5 1580 3510 3120 2.22

120 56.4 1550 3370 2960 2.17

 Results: Double bond
content of the samples

• Ideally each monomer unit contains one double

bond
• Shift of the signal of the proton next to the
double bond is visible in 1H NMR spectrum
• This peaks distinct with peaks of the other
protons
• The double bond content decreases with Average number of double bonds / monomeric unit
increasing reaction time at both concentrations
• Lower double bond ratio at higher SnCl4 cSnCl4 5 min 30 min 60 min 120 min
contentration 114 mM 0.99 0.93 0.88 0.86

157 mM 0.88 0.85 0. 0.69

Conclusion
• Successful poly(β-pinene) production at room
temperature with SnCl4 in BTF solvent
• Conversion rates: 40-47% (115 mM SnCl4);
38-56% (175 mM SnCl4)  full conversion has
not been achieved
• Mn around 2000 g/mol
• Further measurements needed for more
information (e. g. change SnCl4 concentration)
• High double bond content, but decreases with
reaction time  occurrence of side reactions
Acknowledgement

Prof. Iván Béla

Dr. Verebélyi Klára
Thank you for your kind
attention!
 A BENZOTRIFLUORID (BTF)

• Non-toxic
F F
• Not volatile
F
• in many conventional organic and fluorochemical reactions
successfully, e.g. Friedel-Crafts, radical, transition metal-
catalysed reactions [1]
• the radical polymerisation of fluorine-containing monomers
solvent [2]
• Low temperature carbocationic polymerisation solvent of
isobutylene [3]

1. Maul, J. J.; Ostrowski, P. J.; Ublacker, G. A.; Linclau, B.; Curran, D. P. Top. Curr. Chem. 1999, 206, 79-105
2. Ribaut, T.; Desmazes, P.; Fournel, B.; Sarrade, S. J. Polym. Sci. Part A: Polym Chem. 2009, 47, 5448-5460
3. Groh, P. W.; Iván, B.; Szesztay, M.; De Jong, F.; Graafland, T. Polym. Prep. 2000, 41, 1379-1380
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 Formulas for calculations

• Using the mass data of the polymers obtained and the total monomer quantity the conversion is
calculated with the following eguation

• Number average (Mn) and mass average (Mw) molecular weights, which can be calculated using
the following formulae (Mi is the molar mass of a polymer containing i number of monomer units
and ni is the number of polymer chains of molar mass Mi.)

• Polymer dispersity (D) is the value used to characterize the molecular weight distribution of polymer chains

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