Alternating Copolymerization of Limonene Oxide and Tetrahydrophthalic

Anhydride
Katherine Fernandes de Jesus* (PG), Alexandre Carneiro Silvino (PQ)
Instituto de Macromoléculas Professora Eloisa Mano, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ, Brasil
*Katherine_fj@ima.ufrj.br

Introduction
Polyesters can be synthesized by ring-opening copolymerization of anhydrides and epoxides. The use of limonene oxide (OL) in the production of polyesters represents
the possibility of using an interesting and abundant building block in the development of new sustainable materials. Taking into account the wide variety of anhydride
structures available, the options for obtaining new polymers grow enormously.2,3 Among them, anhydrides containing unsaturations such as tetrahydrophthalic and
itaconic anhydride may be used. For the copolymerization reaction with limonene oxide the use of modified cobalt / SALPHEN metal complexes with electron-
withdrawing groups in their structure was not mentioned. These groups can affect the electrophilicity of the metals and consequently the activity of the catalyst.

Goals
Obtain catalysts type SALPHEN of Cobalt with and without the electron-withdrawing Br substituent on its structure and with the t-Bu substituents on the aromatic rings. Moreover to develop
materials based on the copolimerization by ring opening of the limonene oxide and anhydrides, characterize the microstructure of the copolymers and evaluate its thermal properties.

Experimental
Limonene Synthesis of
Inert Synthesis of Copolimerization FTIR
oxide Anhydrides Ligands
atmosphere complexes precipitation RMN
destillation SALPHEN

1,2- Bulk/ GPC

SALPHEN/ cobalt(II)
Schlenk/glove Used as benzenediamine DSC
CaH2 3,5-di-tert-butyl
Acetate CHCl3
bag received tetrahydrate TGA
salicylidene in Pentane

Results and Discussion

Scheme 1. Alternating copolymerization of limonene oxide and Tabela 1. Copolymerization of epoxides with anhydrides in bulk with the Co(III) SALPHEN
tetrahydrophthalic anhydride using Co(III)/SALPHEN catalysts catalyst using PPNCl as a co-catalyst.
Ratio T t Conv.a Mn Tonset Tg
Entry Cat. Epoxide Anhydride PDIb
Ep:An:Cat:Co-cat (oC) (hs) (%) (x103)b (oC)e (oC)f
1c Co1 Lim. None 250:0:1:1 130 24 0 ND ND ND ND
2c Co1 None TH 0:250:1:1 130 24 0 ND ND ND ND
3 Co1 Lim. TH 250:250:1:1 130 24 >99 1.2 1.35 241 60.3
4 Co1 Lim. TH 500:500:1:1 130 24 >99 1.4 1.42 237 47.2
5 Co1 Cicloh. TH 250:250: 1:1 130 24 >99 1.0 1.18 214/302 51.3
6 Co1 Lim. TH 250:250:1:1 110 3 85 1.2 1.27 229 50.9
7 Co2 Lim. TH 250:250:1:1 110 3 78 1.3 1.32 229 43.6
8 Co1 Cicloh. TH 250:250:1:1 110 3 >99 1.0 1.14 220/305 52,3
9 Co2 Cicloh. TH 250:250:1:1 110 3 >99 0.9 1.18 212/302 51.2
10 Co1 Lim. IT 250:250:1:1 130 24 >99 1.0 1.13 229 67.0
11 Co2 Lim. IT 250:250:1:1 130 24 >99 2.1 2.08 233 81.7
12d Co1 Cicloh. IT 250:250:1:1 130 24 ND ND ND ND ND
c,d,e,g aDetermined by 1H-NMR. bDetermined by SEC. cNo polymer was formed. dInsoluble product was formed. eDetermined by TGA.
A B fDetermined by DSC. ND=Not determined

k
h
b
j
c d e
i
f
a
f
b

1H 1H
Figure 3. Comparison of catalysts: Reactions were
Figura 1. A – NMR spectrum of poly(limonene tetrahydrophthalic), Table 1, entry 1. B – NMR spectrum of Fugure 2. FTIR spectra of the monomers and
performed in bulk. Ratio: 250:250:1:1. The vials
poly(cyclohexene tetrahydrophthalic), Table 1, entry 8. the copolymer (Table 1, entry 4)
were heated to 130 °C and for 24 h.

All ligands and complexes were characterized based on the data found in the literature. Table 1 shows the results of molar mass and polydispersion of the obtained polymers
No homopolymer from limonene oxide and tetrahydrophthalic anhydride was obtained in this system. Reactions with cyclohexene oxide, which has lower steric hindrance, showed
conversion above 99% in only 3 hours. The reactions with limonene oxide required longer reaction times. The cobalt 1 catalyst showed higher activity compared to 2. Reactions
between IT and Cicloh. produced insoluble materials that swelled with solvent indicating high cross-linking. The initial degradation temperature showed temperatures slightly
above 200°C. The glass transition values for the polymers with cyclohexene oxide and limonene oxide were around 55°C. The polymers with itaconic anhydride presented higher Tg
values, probably due to cross-linking. The 1H NMR signals indicate that there was no reaction through the double bond.

Conclusion References
1Pereti,K. L.; Ajiro, H.; Cohen, C. T.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem.
The results indicate the formation of polymers by the copolymerization of OL and anhydrides with the two
cobalt complexes used, showing the viability of this route to obtain polyesters with incorporation of Soc. 2005, 127, 11566.
2 Nejad, E. H.; Paoniasari, A.; Melis, C. G. W. V.; Koning, C. E.; Duchateau, R.
partially renewable resources. Further attempts to purify the monomers will be carried out to increase the
molar mass and consequently the thermal properties. Macromolecules.2013, 46, 631.
3 Robert, C..; Montigny, F.; Thomas, C. M. Nature Communications. 2011, 2, 1.

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