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Oxetane-Terminated Telechelic Epoxy-Functional Polyesters as


Cationically Polymerizable Thermoset Resins: Tuning the Reactivity with
Structural Design

Susana Torron, Mats Johansson


Department of Fibre and Polymer Technology, Division of Coating Technology, KTH Royal Institute of Technology, School of
Chemical Science and Engineering, SE-10044 Stockholm, Sweden
Correspondence to: M. Johansson (E - mail: matskg@kth.se)

Received 11 March 2015; accepted 10 April 2015; published online 7 May 2015
DOI: 10.1002/pola.27673

ABSTRACT: A series of epoxy-functional telechelic oligomers spectroscopy revealing a preferred copolymerization when
containing oxetane end groups have been synthesized. The compared with the homopolymerization. By tailoring the differ-
precursor monomer, extracted from outer Birch bark, was first ent structures, it was possible to control the final mechanical
polymerized through enzyme-catalyzed esterification to form properties of the networks. V C 2015 Wiley Periodicals, Inc. J.

oligomers having epoxy and/or oxetane groups in the struc- Polym. Sci., Part A: Polym. Chem. 2015, 53, 2258–2266
tures. The oligoesters were subsequently crosslinked through
cationic polymerization either by epoxy or oxetane homopoly-
merization or copolymerization when both functionalities were KEYWORDS: biobased monomer; cationic polymerization; enzy-
present. A study of the polymerizations of the resins was per- matic catalysis; enzymes; epoxide; oxetane; telechelic
formed “in situ” using real-time Fourier transform infrared polymers

INTRODUCTION The production of materials derived from from adhesives to composites.5 Cationic polymerization of
renewable resources is a field in continued development. ring-opening monomers, such as epoxides or oxetanes, is
The substitution of fossil-based raw materials for other more compared with free radical polymerization of acrylates not
environmentally friendly alternatives is of great interest in affected by oxygen inhibition. Furthermore, ring-opening
terms of costs, degradability, and recyclability. Moreover, the monomers exhibit a lower amount of cure shrinkage. Both
large variety of compounds readily available in nature with these features are of importance in several applications rang-
“inbuilt” functionalities encourages its use as building blocks. ing from thin organic coatings (oxygen inhibition issues) to
One group readily present in nature that can undergo a large dental composites (cure shrinkage).
variety of chemistries are epoxides. Epoxides are present in
To form polymer networks through cationic polymerization
vegetable oils or cork. One example of an epoxy-functional
using epoxy-derived monomers, it is necessary that those
monomer present in nature that has been used as building
monomers possess at least two functionalities as in the case
block for network formation is the 9,10-epoxy-18-hydroxyoc-
of telechelic polymers. By definition, telechelic polymers are
tadecanoic acid (EFA; Fig. 1) that can be retrieved from the
“prepolymers capable of entering into further polymerization
outer bark of the Birch tree.1–3 This monomer is capable to
or other reactions through its reactive end groups.”6 The
undergo a large variety of chemical reactions, for example,
introduction of end functionalities will also increase the
through condensation reaction of the end groups4 or through
options for network formation as different chemistries can
reaction of the epoxide.
be applied to each group.

One of the strategies most frequently used for the prepara- However, the synthesis of telechelic polyesters is not always
tion of thermosets derived from epoxy compounds is cationic easy to accomplish by traditional acid catalysis when dealing
polymerization. One of the key features of cationic polymer- with epoxy derivatives. One way to circumvent this issue is
ization is the possibility of triggering the reaction with UV to make use of selective catalysts such as enzymes. With the
light. The so-called cationic UV curing is extensively used aid of the enzymes, it is possible to synthesize epoxy-
nowadays for the preparation of diverse materials ranging functional polyesters directly from epoxy-functional x-

Additional Supporting Information may be found in the online version of this article.
C 2015 Wiley Periodicals, Inc.
V

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EXPERIMENTAL

Materials
FIGURE 1 9,10-Epoxy-18-hydroxyoctadecanoic acid (EFA)
EFA was extracted from outer birch bark (Betula pendula)
monomer. supplied by Holmen AB (c/o Holmen Energi, SE-89810) as
previously reported in the literature by us and others.14–16
Dimethyl adipate (DA), hexanol, hexadecanedioic acid (99%),
hydroxy fatty acids without altering the epoxide4 or to incor-
ethylene glycol, and immobilized CalB (Novozyme 435) were
porate in the same polymer backbone functional groups that
purchased from Sigma-Aldrich. Trimethylpropyl oxetane
by other synthetic routes would be more difficult to have
(TMPO) was used as received from Perstorp AB. The
simultaneously due to self-reaction of those as a thiol and an
“photoinitiator” Uvacure 1600 was supplied by CYTEC.
alkene.7
Synthesis and Characterization of Telechelic Oligomers
The control of the mechanical properties of the formed ther-
For the synthesis of telechelic polymers containing an epox-
mosets will rely on the possibility of selectively reacting
ide in the backbone, that is, using the EFA monomer as pre-
with the functional groups present in the polymer. Having
cursor, the synthetic route used is similar to the one
functional groups in the main chain and at the ends, that is,
previously reported in the literature.14,17 The enzyme-
in the telechelic positions, increase dramatically the options
catalyzed polymerization is done in bulk and in a “one-pot
of network formation by either reaction of those groups with
synthesis” using the reactants in the adequate stoichiometric
themselves separately or at the same time. These options
ratios depending on the desired degree of polymerization
will increase when the end groups and the ones present in
(DP). The quantities in all polymerizations correspond to an
the main chain are also capable to react with each other,
aimed total yield of 250 mg. The formed oligomers were
that is, to copolymerize with each other. This is the case of
characterized with Fourier transform infrared spectroscopy
epoxides and oxetanes, for example, as shown by Sasaki
(FTIR), 1H NMR, MALDI-TOF MS, and size exclusion chroma-
et al.8 and Crivello et al.,9,10 when a small amount of epoxy
tography (SEC). Detailed assignments can be found in Sup-
monomer is present in the cationic polymerization of an
porting Information.
oxetane-derived monomer, the polymerization rates highly
increase as a consequence of the fast generation of an oxo- Synthesis of a,x-Oxetane End-Capped Epoxy-Functional
nium ion from the epoxy ring (eq 1 and Fig. 2) that gives a Polyester DP3 (EODP3) and DP6 (EODP6)
“kick-start” to the cationic polymerization of the oxetane (eq EFA, DA, and TMPO were put into a 25-mL round-bottomed
2 and Fig. 2).11 flask in a 3:1:2 ratio for DP3 and 6:1:2 for DP6 and heated
Other factors such as the differences in reaction enthalpies up to melting temperature at around 85 8C. Once the reac-
also affect the polymerization rates. This and other studies tants had reached the molten state, the immobilized enzyme
mainly dealing with primary epoxides and oxetane mono- was added (10% of the total amount of monomers), and the
mers clearly show that epoxy and oxirane monomers readily reaction was allowed to proceed at open atmosphere for 2 h.
copolymerize to give polyether polymers with varying ether After that time, the flask was connected to a vacuum line,
segments due to the specific copolymerization rates.12,13 and the reaction was run overnight (Scheme 1).

The incorporation of epoxy- and oxetane-functional groups The reaction was stopped by dissolving the product in chlo-
in the same polyfunctional resin would be an extension of roform and filtering off the immobilized enzyme. The prod-
this concept of copolymerization and give a new platform in uct was characterized and used without further purification
designing thermoset network structures. (yield of EODP3: 94%; yield of EODP6: 65%).

This study aims to describe the concept of incorporation of Synthesis of a,x-Hexane End-Capped Epoxy-Functional
two different functional groups capable of copolymerizing Polyester DP3 (EDP3)
into telechelic oligomers as a tool of tailoring the final ther- EFA, DA, and hexanol were put into a round-bottomed flask
moset properties. in a 3:1:2 ratio and heated up to 85 8C. After the reaction

FIGURE 2 Initiation of the cationic polymerization of oxetanes SCHEME 1 Reaction scheme for the formation of oligomers
by reaction with an oxonium ion (AX, photoinitiator). EODP3 and EODP6.

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tate was filtered out and dried under vacuum to yield a


white powder.

Yield: 69%. 1H NMR (400 MHz, CDCl3, d): 1.23–1.26 (20H,


m, ACH2A), 1.60 (4H, m, ACH2ACH2ACOA, J 5 7.2), 2.28
(4H, t, ACH2ACOA, J 5 7.6), 3.64 (6H, s, CH3OA).
SCHEME 2 Reaction scheme for the formation of oligomer
Network Formation
EDP3.
The cationically crosslinked networks were prepared in all
cases from a mixture containing 25 mg of each oligomer, 4%
(w/w) of the photoinitiator (Uvacure 1600), and 100 mg of
mixture had reached that temperature, the enzyme was
chloroform. For the photo real-time infrared (photo-RTIR)
added to the flask (10% of the total amount of monomers),
measurements, the networks were formed in situ on the sur-
and the reaction was allowed to proceed at open atmosphere
face of the attenuated total reflection (ATR) crystal of the
for 2 h and afterward under vacuum overnight (Scheme 2).
FTIR after evaporation of the solvent and continuous expo-
The reaction was stopped by filtering out the enzyme, and sure to the UV light with an intensity of 10 mW/cm2 for a
the product was characterized and used without further period of 1 h. The rest of the films were prepared by solvent
purification (yield: 65%). casting of the mixture on a glass substrate with the aid of a
pipette. After evaporation of the solvent, the mixtures were
covered with a quartz microscope slide to obtain homogene-
Synthesis of a,x-Oxetane End-Capped Aliphatic Polyester ously cured films. Free-standing films were obtained after 15
DP3 (ODP3) min of exposure to UV light with an intensity of 20 mW/cm2
To prepare the aliphatic homologous of the polyester with (dose: 18 J/cm2). The time of exposure was selected from
DP3, end capped with oxetane, hexadecanedioic acid was the results obtained after the real-time FTIR (RT-FTIR)
chosen as monomer. Because of the nonsolubility of this studies.
monomer in any suitable solvent for the enzymatic polymer-
ization, the equivalent methyl ester was prepared prior to Analytical Methods
polymer formation (Scheme 3). 1
H NMR
The spectra were recorded at 400 MHz on a Bruker AM 400
Dimethyl hexadecanedioate, ethylene glycol, TMPO, and using deuterated chloroform (CDCl3) as solvent. The solvent
molecular sieves of 4 Å (25 wt % of the total amount of signal was used as reference.
monomers) were put into a round-bottomed flask in a 3:2:2
ratio and heated up to 85 8C. After the reaction mixture had MALDI-TOF MS
reached that temperature, the enzyme was added to the flask MALDI-TOF MS spectrum acquisitions were conducted on a
(10% of the total amount of monomers), and the reaction Bruker UltraFlex MALDI-TOF MS with SCOUT-MTP Ion
was allowed to proceed at open atmosphere for 2 h and Source (Bruker Daltonics, Bremen) equipped with a N2 laser
afterward under vacuum overnight. The reaction was (337 nm), a gridless ion source, and reflector design. All
stopped by filtering out the enzyme. The product was puri- spectra were acquired using a reflector-positive method with
fied by column chromatography using silica as stationary an acceleration voltage of 25 kV and a reflector voltage of
phase and a gradient of eluents, starting with a mixture of 26.3 kV. The detector mass range was set to 200–2500 m/z.
ethyl acetate:heptane 30:70 and increasing to 100% ethyl A THF solution of 2,5-dihydroxybenzoic acid was used as
acetate (yield: 11%). matrix. The obtained spectra were analyzed with FlexAnaly-
sis Bruker Daltonics, Bremen, version 2.
Synthesis of Dimethyl Hexadecanedioate
Hexadecanedioic acid (3.5 mmol, 1 equiv) was suspended in Size Exclusion Chromatography
methanol (20 mL). Afterward, HCl (2.2 equiv) was added SEC using DMF (0.2 mL/min) with 0.01 M LiBr as the mobile
dropwise at room temperature. After 4 h, the formed precipi- phase was performed at 50 8C using a TOSOH EcoSEC HLC-
8320GPC system equipped with an EcoSEC RI detector and
three columns (PSS PFG 5 lm; microguard, 100 Å, and 300
Å; MW resolving range: 100–300,000 g/mol) from PSS
GmbH. A calibration method was created using narrow linear
polystyrene standards. Corrections for the flow rate fluctua-
tions were made using toluene as an internal standard.

Fourier Transform Infrared Spectroscopy


FTIR analysis was carried out using a Perkin-Elmer Spec-
trum 2000 FTIR instrument (Norwalk, CT) equipped with a
SCHEME 3 Reaction scheme for the formation of oligomer single reflection (ATR) accessory unit (Golden Gate) from
ODP3. Graseby Specac LTD (Kent, England) and a TGS detector

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using the Golden Gate setup. Each spectrum collected was


based on 16 scans averaged at 4.0 cm21 resolution range of
600–4000 cm21. Data were recorded and processed using
the software Spectrum from Perkin-Elmer UV light sources.
The light source used for the crosslinking of the films was a
Black Ray B-100AP (100 W, k 5 365 nm) Hg UV lamp with
an irradiance of 21 mW/cm2 as determined with an UVI-
CURE Plus High Energy UV integrating radiometer (EIT,
USA), measuring UVA at 320 nm  k  390 nm. The light
source used for the photo-RTIR measurements was a Hama-
matsu L5662 equipped with a standard medium pressure
200-W L6722-01 Hg–Xe lamp and provided with optical
fibers. The UV intensity was measured using a Hamamatsu
UV light power meter (model C6080-03) calibrated for the
main emission line centered at 365 nm. The intensity of the
lamp was 7 mW/cm2.

Real-Time FTIR Analysis


The RTIR analysis was made using a Perkin-Elmer Spectrum
2000 FTIR instrument (Norwalk, CT) equipped with a single FIGURE 3 a,x-Functionalized telechelic polyesters.
reflection (ATR) accessory unit (Golden Gate) from Graseby
Specac LTD (Kent). RT-FTIR continuously recorded the chem-
ical changes over the range 4000–600 cm21. Spectroscopic Characterization of Telechelic Oligomers
data were collected at an optimized scanning rate of 1 scan To confirm the formation of the telechelic polyesters, 1H
per 1.67 s with a spectral resolution of 4.0 cm21 using Time NMR spectroscopy, MALDI-TOF, and SEC analysis were per-
BaseVR software from Perkin-Elmer. formed. As exemplified in Figure 4 (see also Supporting
Information Figs. SI3–SI6), the success in the synthesis of
the EODP3 polymer is confirmed by the appearance of new
Dynamic Mechanical Thermal Analysis signals: p, q, and r, at around 2.3, 4, and 4.2 ppm, respec-
The study of the physical properties of the polymerized resins tively, as a result of the formation of two new ester bonds
was performed on a Q800 dynamic mechanical thermal ana- between the EFA monomer and the DA, and the EFA mono-
lyzer (TA Instruments), equipped with a film fixture for tensile mer and the TMPO. At the same time, the peak correspond-
testing. The measurements were done between 260 8C and ing to the methyl group of the DA, peak k, disappears as
150 8C, with a heating rate of 5 8C/min. The tests were per- methanol is formed and eliminated as a byproduct of the
formed in controlled strain mode with a frequency of 1 Hz, an esterification. It is also noteworthy that the epoxide is kept
oscillating amplitude of 5 lm, and a force track of 125%. intact during the synthesis, as confirmed by peak i.

Although the a,x-difunctional oligomers are obtained in


RESULTS AND DISCUSSION majority, a fraction of monosubstituted oligomers is also
Synthesis of Telechelic Oligomers obtained as confirmed by MALDI-TOF MS (Supporting Infor-
To understand how the polymer network is formed when mation Figs. SI7–SI10). The DP was calculated from the 1H
the two cyclic ethers capable to undergo cationic polymeriza- NMR spectra as the relationship between the peaks of the
tion in similar manners are present in the system, telechelic repeating unit and the end capper. The results are summar-
oligomers with and without an epoxide built in the backbone ized in Table 1.
and/or end capped with an oxetane were synthesized. In Fig- The values obtained for the degrees of polymerization are
ure 3, all the oligomers used in this work are depicted. coherent with the molecular weight distributions obtained with
The utilization of immobilized enzymes as catalysts not only MALDI-TOF analysis (Supporting Information Figs. SI7–SI10).
afford very mild conditions to be used but also make the
product purification very simple as the catalyst is easily Network Formation and Final Properties
removed by filtering it off. The final structure can also be In general terms, when two or more functional groups are
easily adjusted by appropriate choice of the in-going stoichi- present in the polymer chain, the reaction between them-
ometry of the reactants. The variation in degree of di-end- selves or of those with a crosslinker yields thermoset forma-
functionalization is within the normal range for this type of tion. In the case of the networks formed through cationic
systems. This study did not include efforts in optimizing the polymerization, a strong nucleophile is first needed to form
synthesis toward 100% di-end-functionalization as the the oxonium ion that will subsequently initiate the propaga-
obtained percentages were considered to be high enough for tion reactions through ring opening of the cyclic ethers
the purpose of the study. (Fig. 2). The most common initiators used in cationic ring

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FIGURE 4 1H NMR spectra of the EODP3 oligomer before (lower spectrum) and after reaction (upper spectrum).

opening of cyclic ethers consist of diaryliodonium18 or triar- Polymerization Performance


ylsulfonium19 salts. For the oligomers with both epoxide and As aforementioned, for the better understanding of the pro-
oxetane groups in the main chain, three possibilities for ther- gress of the reaction, four different oligomers were synthe-
moset formation were contemplated: cationic homopolymeri- sized prior crosslinking. For the polymers containing both
zation of the epoxy group with itself, of the oxetane with
itself, and copolymerization by reaction of the epoxide with
oxetane or vice versa. Although the epoxide is slightly more
ring strained than the oxetane and will ring open faster
when attacked by a nucleophile, the oxetane is slightly more
basic which will make it more reactive toward cationic poly-
merization;20 therefore, the three contemplated possibilities
were considered equally probable. Most previous studies on
the copolymerization of oxetanes and epoxides have further-
more been performed on primary epoxides being more reac-
tive than the secondary epoxides used in the current study.11
However, because of the different nature of the system con-
sidered in this study, this assumption cannot be directly
applied. RT-FTIR studies and dynamic mechanical analysis
(DMA) were performed to further understand how the net-
works were formed.

TABLE 1 Degrees of Polymerization and Percentage of End


Functionalization for the Different Di-End-Functionalized
Oligomers Calculated from Their 1H NMR Spectrum

Oligomer DPNMR % Di-End-Functionalized

EODP3 2.2a 71e


b
EODP6 5.1 89f
c
EDP3 2.7 99g
FIGURE 5 Schematic representation of the formation of the
d
ODP3 2.3 NA polymer thermoset by reaction of the epoxides, and FTIR spec-
tra of the EDP3 oligomer taken every 10 min with focus in the
Calculated from the relationship between peaks: a i 3 2 5 r 3 DP; b i 3
2 5 q 3 DP; c i 3 2 5 (q 2 i) 3 DP; d h 3 2 5 i 3 DP.
region between 1120 and 1000 cm21 (PI, photoinitiator). [Color
Calculated from the relationship between peaks: e (m, m0 ) and q; f (m, figure can be viewed in the online issue, which is available at
m0 ) and p; g (q 1 p) and i. NA, not applicable due to peak overlapping. wileyonlinelibrary.com.]

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epoxides and oxetanes, two possibilities were contemplated:


homopolymerization and copolymerization.

To be able to discriminate the peaks corresponding to the


homopolymerization, homologous oligomers only containing
epoxides and only containing oxetanes were synthesized.
Homopolymerization of secondary epoxides giving a substi-
tuted polyethylene glycol structure give rise to a new
absorption band at 1073 cm21 (Fig. 5), whereas homopoly-
merization of the oxetane on the other hand will yield a new
band at 1062 cm21 (Fig. 6) corresponding to a polypropyl-
ene glycol structure. The polymerization of resins EODP3
and EODP6, however, gave rise to a much more complex
absorption pattern in the ether region, which strongly indi-
cates that a copolymerization is preferred (Fig. 8).

As can be seen in Figures 5 and 6, the cationic polymeriza-


tion of the oligomer only containing epoxy groups (EDP3) is
faster than the one of the oligomer only containing oxetanes
(ODP3). Although these results are qualitative and no quanti-
tative kinetic studies have been performed, it is possible to
see that after 30 min all the epoxides have reacted while the
oxetane is still reacting as seen by a continued increase in
the peak at 1062 cm21.

It is also noteworthy that in the first 10 min of the polymer-


ization of the ODP3 polymer, the peak at 1117 cm21 appears
at the same time as the one at 1107 cm21 disappears (Fig.
6, squared). After that time, the peak at 1107 cm21 varies
less, whereas the rest of the peaks at around 1062 cm21
seemingly increase to a larger extent. This can be explained
as in the first 10 min, there is a continuous generation of ali-
FIGURE 6 Schematic representation of the formation of the poly-
phatic ethers (peak at 1117 cm21) originated from the ring
mer thermoset by reaction of the telechelic oxetanes, and FTIR
opening of the cyclic oxetanes (peak at 1107 cm21).
spectra of the ODP3 oligomer taken every 10 min with focus in
the region between 1120 and 1000 cm21. Squared: spectra taken As can be seen in Figure 7, after this time the generation of
every 10 s during the first 10 min for the region between 1120 aliphatic ethers continues at a slower rate indicating that
and 1080 cm21 (PI, photoinitiator). [Color figure can be viewed in
other factors such as molecular mobility and dilution effects
the online issue, which is available at wileyonlinelibrary.com.]
starts to have increased influence.

FIGURE 7 Absorbance versus time for the two different peaks of ODP3 enhanced at the right side. [Color figure can be viewed in
the online issue, which is available at wileyonlinelibrary.com.]

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FIGURE 8 Schematic representation of the formation of the polymer thermoset by copolymerization between epoxides and oxe-
tanes, and FTIR spectra of the EODP3 and EODP6 oligomers taken every 10 min with focus in the region between 1120 and
1000 cm21 (PI, photoinitiator). [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

Because of the overlapping peaks, it is difficult to assess the suppressed as the peak at 1073 cm21 is no longer the one
different peaks in the area between 1300 and 1000 cm21 for governing this region of the spectra.
the EODP3 oligomer. However, it is possible to observe the
success of the cationic polymerization as new peaks appear It is also worth highlighting that when the variation in
already after some minutes of irradiation. These new absorp- absorbance as a function of the reaction time of the peak at
tion suggest that there is a complex mixture of different 1062 cm21 is compared with the different oligomers con-
reaction sequences present in the formation of the network taining oxetanes (Fig. 9, left), there is a clear increase in the
structure and that the homopolymerization of the epoxide is reaction rate for the oligomers containing both oxetane and

FIGURE 9 Absorbance versus time for the 1062 and 1073 cm21 peaks. [Color figure can be viewed in the online issue, which is
available at wileyonlinelibrary.com.]

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TABLE 2 Summary of the Mechanical Properties of the


Oligomers

Oligomer Tg (8C) tan d (E0 /E00 ) E0 (GPa)a E0 rp (GPa)b

EDP3 5 0.51 2 0.3


EODP3 15 1.03 2 1
EODP6 12 0.79 2 0.2

a
E0 : storage modulus at 260 8C.
b
E0 rp: storage modulus in the rubbery plateau.

opposite trend. The most interesting feature is that the tan d


curve narrows and increases in height with increased cross-
link density. The normal trend is that the transition is broad-
ened and that the peak height decreases. This implies that
FIGURE 10 Tan d versus temperature for cured resins EDP3, the network formation routes are different for the different
EODP3, and EODP6. [Color figure can be viewed in the online resins, that is, the polymerization mechanism differs from
issue, which is available at wileyonlinelibrary.com.] homopolymerization of epoxides (EDP3) to mixed epoxy
homopolymerization/copolymerization (EODP6), and mainly
epoxide. The increase is much higher for the oligomer with epoxy–oxetane copolymerization (EODP3). A more narrow
DP3 than for the one with DP6 (Fig. 9). This can be transition indicates a more homogeneous network structure
explained as the epoxy:oxetane ratio for the polymer with with high regularity in the network. This type of change is
DP3 is higher than for the polymer with DP6 (3:2 and 3:1, often seen when changing the reaction mechanism going
respectively) and would also confirm the hypothesis of the from a chainwise to a stepwise mechanism as in the case of
increase in reaction rate due to copolymerization between comparing free radical acrylate polymerization (chainwise)
those polymers. The same trend is observed for the peak at to thiol-ene systems (stepwise).21
1073 cm21 (Fig. 9, right), although the difference in the reac-
tion rate between EODP3 and EDP3 is not as big as for the The crosslink density is also directly related to the rubbery
previous case. It should, however, be noted that the very modulus, and it is clearly seen that EODP3 is more crosslinked
broad and overlapping peaks only allow for a qualitative than the others (Table 2 and Supporting Information Fig. SI16).
evaluation of the rate differences. The FTIR spectra before The difference between EODP6 and EDP3 is not significant
and after polymerization of the oligomers can be found in enough to be validated by the rubbery modulus level because
the Supporting Information. of the experimental uncertainties, that is, the level of uneven-
ness of the films was too large. More studies are, however,
Mechanical Properties of the Networks needed to further elaborate on details of the copolymerization
To support the conclusion that the telechelic end groups mechanism, and this is out of scope of the current study.
(oxetanes) do connect to the main chain in the telechelic,
DMA was performed. For all cases except of the ODP3 poly- CONCLUSIONS
mer, free-standing films were obtained allowing mechanical In this work, the synthesis of a series of telechelic polyesters
analysis to be performed. The initial resin structure as well and their consecutive incursion into a polymer network is
as the different ways the networks are formed, that is, homo- presented. The intrinsic epoxy functionality of the precursor
polymerization or copolymerization, will result in different monomer (EFA), first extracted from outer Birch bark, is pre-
mechanical performances of the films. The main factors served with the aid of enzymatic catalysis.
affecting the mechanical performance of a thermoset are the
rigidity of the backbone, the polarity, the crosslink density, By understanding how the different groups present in the
and the presence of loose chain ends. The homogeneity of polymer chain react with each other, it will be able to predict
the network is furthermore reflected in the width of the Tg the final properties of the network.
transition. All the present resins are aliphatic polyesters
crosslinked with ether linkages, and hence, there is a similar- Recently, our group reported the lipase-catalyzed synthesis of
ity in polarity and rigidity of the backbone. When analyzing methacrylate end-capped EFA oligoesters and their subsequent
the tan d, a clear trend is seen as an increased peak temper- polymerization for network formation.14 The groups were
ature value going from EDP3 to EODP6 to EODP3 is reacted either separately or in parallel using different polymer-
observed (see Fig. 10 and Table 2). ization techniques, that is, radical polymerization or cationic
polymerization. The different ways these groups were cova-
This is normal for polymers with a similar backbone struc- lently linked to each other had direct repercussion on the prop-
ture and associated with an increased crosslink density. An erties of the formed networks, which could be seen as a
increase of unreacted chain ends will, however, lead to an variation on the mechanical properties of the network.

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In this work, we extend this concept by increasing the possi- 6 IUPAC. Compendium of Chemical Terminology, 2nd ed. In
bilities for network formation. In this case, an oxetane was IUPAC (the “Gold Book”). Compiled by A. D. McNaught and A.
introduced as end capper of the enzyme-catalyzed esterifica- Wilkinson. Blackwell Scientific Publications, Oxford, UK 1997.
tion. As previously reported in the literature, oxetanes and 7 M. Takwa, K. Hult, M. Martinelle, Macromolecules (Washing-
ton, DC) 2008, 41, 5230–5236.
epoxides are capable to copolymerize with each other. How-
8 H. Sasaki, J. M. Rudzinski, T. Kakuchi, J. Polym. Sci. Part A:
ever, to our knowledge, this concept had never been applied
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for polymers containing these compounds in the same back-
9 U. Bulut, J. V. Crivello, J. Polym. Sci. Part A: Polym. Chem.
bone. As proven in this work, these two compounds not only
2005, 43, 3205–3220.
do copolymerize but also this reaction is preferred, seen as
10 J. V. Crivello, B. Falk, M. R. Zonca, Jr., J. Polym. Sci. Part A:
an increase in the reaction rates in comparison with the Polym. Chem. 2004, 42, 1630–1646.
homopolymerizations. 11 J. V. Crivello, J. Polym. Sci. Part A: Polym. Chem. 2014, 52,
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12 S.-C. Yang, J.-H. Jin, S.-Y. Kwak, B.-S. Bae, J. Appl. Polym.
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ACKNOWLEDGEMENTS
13 J. V. Crivello (Rensselaer Polytechnic Institute). U.S. Patent
This work received funding from the People Programme 20060041032-A1, 2006.
(Marie Curie Actions) of the European Union’s Seventh 14 S. Torron, S. Semlitsch, M. Martinelle, M. Johansson, Mac-
Framework Programme FP7/2007 2013/ under REA grants romol. Chem. Phys. 2014, 215, 2198–2206.
agreement number 289253. The authors thank Stefan Sem- € diger, P. Hendil-Forssell, C. Hedfors, M. Martinelle, S.
15 A. Ru
Trey, M. Johansson, J. Renew. Mater. 2013, 1, 124–140.
litsch and Mats Martinelle for fruitful discussions about
enzymatic catalysis. 16 T. Iversen, H. Nilsson, A. Olsson (Innventia AB, Sweden).
WO Patent 2010093320-A1, 2010.
17 S. Semlitsch, S. Torron, M. Johansson, M. Martinelle,
unpublished work.
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