Antoine
Adjaoud
ab,
Acerina
Trejo-Machin
ab,
Laura
Puchot
a and
Pierre
Verge
*a
aLuxembourg Institute of Science and Technology, Materials Research and Technology Department, 5 Avenue des Hauts-Fourneaux, L-4362 Esch-sur-Alzette, Luxembourg. E-mail: pierre.verge@list.lu
bUniversity of Luxembourg, 2, Avenue de l'Université, L-4365 Esch-sur-Alzette, Luxembourg
First published on 14th May 2021
This work explores a new strategy, aiming for the synthesis of catalyst-free vitrimers by taking advantage of the abundant number of tertiary amines covalently bound into a polybenzoxazine network. A bio-based monomer was obtained by reacting 4,4-bis(4-hydroxyphenyl)valeric acid, polyethylene glycol, paraformaldehyde and mono-ethanolamine, via consecutive solvent-free Fischer esterification and Mannich-like ring-closure. The two-step reaction led to the formation of quadri-telechelic benzoxazine-terminated polyethylene glycol monomers, containing ester bonds and aliphatic hydroxyl groups. The structural features of the resulting products were substantiated by 1H NMR, 13C NMR, elemental analysis, and FTIR. The occurrence of the thermally induced ring-opening polymerization was monitored by rheological measurements and DSC. At 140 °C, the monomers show a short gelation time (145 seconds). Once polymerized, the polybenzoxazine exhibits a relatively high temperature of α mechanical relaxation (93 °C). Due to the ability of tertiary amines to catalyze transesterification reactions, and to the abundant number of hydroxyl groups, the material enables exchange reactions without the use of an external catalyst. It possesses all the typical characteristics of a vitrimer, such as recycling, reshaping, and self-healing. Short stress-relaxation times were measured (116 s at 170 °C). Finally, the effect of the structural features of the vitrimer was investigated by tuning the crosslinking density of the network and the number of hydroxyl groups, shedding more light on the mechanism of self-catalysis and the range of properties. Therefore, such a strategy constitutes an efficient and versatile route for an easy elaboration of mono-component, catalyst-free, and fast responsive vitrimers.
The different strategies and methodologies conceived to design performant vitrimers can be found in the excellent reviews published by Du Prez et al.,8–11 and Hillmyer and Dichtel.12 Among these strategies, the dynamic transesterification reaction (TER) occurring between ester bonds and hydroxyl (–OH) groups has been reported as the most representative chemistry for driving vitrimer behaviors. In most cases, the TER requires the use of an external catalyst to trigger fast enough exchange reactions within a reasonable range of conditions. Numerous catalysts can be employed to control the transesterification reaction,13 but solid or organic basic catalysts are preferred within a context of vitrimer material elaboration. Among them, zinc acetate (Zn(OAc)2) is the most widely used, owing to its high efficiency.5–7 Tertiary amine (NR3) groups are also well-known sites of TER catalysis.13–15 In one of their pioneering works, Leibler et al. evidenced that triazobicyclodecene (TBD), a bicyclic base containing a NR3 group, gave similar results to Zn(OAc)2.5 Later, Williams et al.,16 and more recently Zhang et al.,17 have both demonstrated in elegant approaches that NR3 covalently bound to the polymer network exert an internal catalysis on the transesterification reactions occurring in epoxy-acid systems. These studies join other recent research works dedicated to the development of internally catalyzed (or catalyst-free) vitrimers.18–22 It is noteworthy that in the absence of a catalyst, the lifetime of a vitrimer relying on a transesterification mechanism could be greatly enhanced, particularly as the risk of ester hydrolysis would be reduced.8 Thus, the elaboration of catalyst-free vitrimers appears of great importance, and the use of polymer structures containing tertiary amines seems to be a reasonable choice.
Polybenzoxazines (PBZs) are mono-component thermoset, polymers constituted of an abundant number of NR3 coming from the auto-catalyzed ring-opening polymerization (ROP) of benzoxazines.23 They are also a promising alternative to phenolic and epoxy resins thanks to their unique mechanical and thermal properties, such as a high glass transition temperature, near-zero shrinkage upon polymerization, and high char yield polymers.24 Benzoxazine monomers are obtained from the condensation reaction of a phenolic compound, a primary amine and paraformaldehyde (PFA). For the past ten years, there has been an explosive growth of research works on polybenzoxazines, dedicated to the use of natural phenolic compounds and amines25–43 as synthons of their monomers. As PFA can be synthesized from bio-ethanol or carbon dioxide, these precursors could be considered as 100% bio-based.44 However, to solve the concern of its carcinogenetic, its substitution by more friendly aldehydes has been under the spotlight of very significant investigations.45,46 It makes no doubts that polybenzoxazines with an excellent life cycle impact will emerge in the coming years.
As they are constituted from a permanent covalent network, PBZs suffer from similar drawbacks to traditional thermoset resins, and they cannot be recycled or reprocessed if they have not been specifically designed with this aim. Few works address this issue, mostly those written by Yagci and Kiskan.47–49 Recently, Verge et al. developed the first vitrimer involving PBZs, showing recyclability, reshaping, and reversible adhesion properties.50 The rearrangement of the permanent network was possible thanks to exchangeable disulfide bonds. However, to the best of our knowledge, none of the self-healable or reprocessable PBZs reported so far demonstrate vitrimer features from TER exchanges. Besides this, and more importantly, the NR3 generated during the ROP of benzoxazines have never been considered as internal catalysts for TER exchanges.
Inspired by a bio-based PBZ we developed in the past,51 and motivated by the outstanding achievements made on vitrimers over the past decade, this work attempts to illustrate how PBZs could be used to design catalyst-free vitrimers based on a transesterification mechanism. 4,4-Bis(4-hydroxyphenyl)valeric acid, more commonly known as diphenolic acid (DPA), is a bio-based diphenol coming from levulinic acid, a chemical extracted from lignocellulosic biomass.52 DPA was used to esterify the end-chains of polyethylene glycol (PEG) to form a quadri-telechelic phenol-terminated PEG (PEG-DPA) containing ester bonds. Thus, the hydroxyphenyl moieties were reacted via a Mannich-like condensation with mono-ethanolamine (mea), an amine derived from L-serine, sorbitol or glycolaldehyde.53,54 This reaction led to the formation of PEG-DPA-mea, a quadri-telechelic benzoxazine-terminated polyethylene glycol monomer with pending aliphatic –OH groups connected to the nitrogen atom (in β-position). These –OH groups were expected to transesterify with the ester bonds. The following paragraphs describe the synthesis of a series of bio-based material and the evidence that their vitrimer behavior does not require the use of an external catalyst. These materials fit many of the Green Chemistry and Engineering principles, such as “Use of renewable feedstocks”, “Safer solvents and auxiliaries”, “Durability rather than immortality”, “Renewable rather than depleting”, and “Design for Commercial after-life”, to cite but a few.
Fourier transform infrared spectroscopy (FTIR) was conducted on a Bruker TENSOR 27 instrument in the attenuated total reflection (ATR) mode using a diamond crystal. All spectra were recorded at room temperature in direct absorbance mode across 4000–400 cm−1 frequency range (32 scans, 4 cm−1 spectral resolution).
Elemental analysis (CHNS measurements) was performed on a Vario MACRO cube CHNS/O from Elementar France SARL. Samples were put into an oxygen-enriched furnace at 1150 °C, where a combustion process converted carbon-to-carbon dioxide; hydrogen to water; nitrogen-to-nitrogen gas/oxides of nitrogen and sulfur-to-sulfur dioxide. The combustion products were swept out of the combustion chamber by an inert carrier gas (He, 600 mL min−1) and passed over heated (850 °C) high purity copper. The separation of the measuring components took place as follows: nitrogen (N2) was not adsorbed in the adsorption columns and was the first measuring component to enter the thermal conductivity detector directly. The other components were adsorbed in their respective adsorption column. Each of these columns was then heated separately to the corresponding desorption temperature (Tdesorpt.) in order to release the components in the following order: CO2 (Tdesorpt. = 240 °C), H2O (Tdesorpt. = 150 °C) and SO2 (Tdesorpt. = 100 °C or 230 °C). After desorption, each component was transported by the carrier gas flow into the measuring cell of a thermal conductivity detector (TCD).
Differential scanning calorimetry (DSC) thermograms were recorded on a Netzsch DSC 204 F1 Phoenix device in standard pierced aluminum crucibles (40 μL). A linear heating ramp from −25 to 300 °C at 10 °C min−1 rate was applied under inert atmosphere (N2). The DSC thermogram of the PBZ material was recorded over two consecutive heating–cooling cycles from −25 to 250 °C (heating rate of 10 °C min−1 and cooling rate of 20 °C min−1) to determine the glass transition (Tg) of the polymer and to ensure complete polymerization.
Thermogravimetric analysis (TGA) was completed on the Mettler Toledo TGA 2 device in standard ceramic alumina pan from 25 to 800 °C at 10 °C min−1 rate under air or inert atmosphere (N2). The maximum of the degradation temperature was determined using the derivative of the TGA curve (DTG).
Rheological measurements were recorded using an Anton Paar Physica MCR 302 rheometer equipped with a CTD 450 temperature control device. Stress relaxation experiments were performed on disk-shaped solid geometry with a disposable aluminum plate–plate (ϕ = 25 mm). The relaxation modulus was followed as a function of time for 2000 s between 120 °C and 170 °C with a constant applied strain of 1% and normal force of 20 N. The original relaxation modulus (G0) was extracted from the initial plateau of the stress relaxation curves (onset point of the second derivative curve). For the isothermal rheo-kinetic measurements, small quantities of the samples were loaded in a parallel plate-plate geometry (ϕ = 25 mm). The polymerization measurements were recorded in the oscillation mode at a frequency of 1 Hz and a controlled strain of 0.1%. Heating ramps of 20 °C min−1 were applied to reach a temperature of 140 °C. The sample deformation was ramped linearly from 1% to 0.2% to remain within the instrument's limitation and to maintain a linear viscoelastic behavior as the moduli (G′ storage modulus, G′′ loss modulus) increase by several orders of magnitude upon curing. The gap between the plates was maintained at 0.5 mm during all the experiments. Rheology temperature sweep curves were performed on the bar-shaped solid in rectangular-torsion mode under constant deformation of 0.1% (1 Hz).
Dilatometry thermogram was recorded on the Netzsch DIL 402 C apparatus from 25 to 200 °C (2 °C min−1) under an inert atmosphere (N2) and a constant force to avoid buckling (30 cN). The material was introduced in a hollow cylinder capped at the extremities by two solid cylindrical end pieces to limit the side expansion.
Dynamic mechanical analysis (DMA) was used to evaluate the mechanical properties of the material after reprocessing. The cured and reprocessed materials were analyzed at room temperature (RT) in tension and in single cantilever mode (effective lengths of 10 and 5 mm, respectively, width 5 mm, thickness 1.25 mm). The measurements were performed at 1 Hz using a preload force of 0.05 N and a sinusoidal strain of 10 μm. The storage modulus (E′) was recorded as a function of time. The reported values are an average of three values.
Optical microscopy was used to illustrate the self-healing performance of the PBZ vitrimer. The surface morphology of scratched samples was examined using the Nikon Universal Design Microscope UDM ECLIPSE LV100D-U (optics ×20, gain ×2.40, exposure 6 ms). The healing process was conducted at 150 °C in a convection oven. The width of the crack was measured before and after the healing process in a dynamic contrast mode at different time intervals.
Swelling experiments were conducted in acetone, chloroform and water by immersion at room temperature of 25 mg of the material in 2 mL of solvent at different time intervals for poly(PEG400-DPA-mea). The crosslinking density was measured by swelling tests in water at different time intervals. The swelling ratio (W) is determined according to the eqn (1):
(1) |
(2) |
(3) |
(4) |
13C NMR (DMSO-d6, 600 MHz, 298°K): δ (ppm) = 27.7 [e]; 30.3 [b]; 36.7 [c]; 44.3 [d]; 63.6 [2]; 68.7 [1]; 70.2 [3]; 115.2 [h]; 128.2 [g]; 139.7 [f]; 155.5 [i]; 173.5 [a].
13C NMR (DMSO-d6, 600 MHz, 298°K): δ (ppm) = 27.7 [e]; 30.3 [b]; 36.7 [c]; 44.3 [d]; 63.6 [2]; 68.7 [1]; 70.2 [3]; 115.1 [h]; 128.2 [g]; 139.6 [f]; 155.5 [i]; 173.5 [a].
FTIR (cm−1); very strong (vs), strong (s), medium (m), weak (w), broad (br): 3339 (–OH stretching, br), 2869 (C–H stretching, vs), 1730 (CO stretching from the ester, s), 1625–1475 (CC stretching vibrations from the aromatic ring, m), 1175 (phenol C–O stretching and –OH in plane deformation, w), 1083 (C–O stretching from the ester, s).
13C NMR (DMSO-d6, 600 MHz, 298°K): δ (ppm) = 27.7 [e]; 30.3 [b]; 36.7 [c]; 44.3 [d]; 63.6 [2]; 68.7 [1]; 70.2 [3]; 115.1 [h]; 128.2 [g]; 139.6 [f]; 155.5 [i]; 173.5 [a].
13C NMR (DMSO-d6, 600 MHz, 298 K): δ (ppm) = 27.5 [e]; 30.3 [b]; 36.5 [c]; 44.5 [d]; 50.6 [m]; 54.0 [n]; 60.0 [o]; 63.6 [2]; 68.7 [1]; 70.2 [3]; 83.1 [l]; 115.9 [i]; 120.3 [k]; 126.0 [g]; 126.6 [h]; 140.8 [f]; 152.3 [j]; 173.5 [a].
13C NMR (DMSO-d6, 600 MHz, 298 K): δ (ppm) = 27.5 [e]; 30.3 [b]; 36.5 [c]; 44.5 [d]; 50.6 [m]; 54.0 [n]; 60.0 [o]; 63.7 [2]; 68.7 [1]; 70.2 [3]; 83.1 [l]; 116.0 [i]; 120.3 [k]; 126.0 [g]; 126.6 [h]; 140.8 [f]; 152.3 [j]; 173.5 [a].
FTIR (cm−1); very strong (vs), strong (s), medium (m), weak (w), broad (br): 3339 (–OH stretching, br), 2869 (C–H stretching, vs), 1730 (CO stretching from the ester, s), 1625–1475 (CC stretching vibrations from the aromatic ring, m), 1230 (C–O–C oxazine asymmetric stretching, m), 1083 (C–O stretching from the ester, s), 1030 (primary alcohol C–O stretching and –OH in plane deformation, w), 928 (C–H out-of-plane vibration in the trisubstituted benzene ring, m).
Elemental analysis (exp, th): C (67, 68), H (150, 98), N (4, 4), S (<0.05, 0).
13C NMR (DMSO-d6, 600 MHz, 298 K): δ (ppm) = 27.6 [e]; 30.3 [b]; 36.6 [c]; 44.5 [d]; 50.6 [m]; 54.0 [n]; 60.0 [o]; 63.7 [2]; 68.7 [1]; 70.3 [3]; 83.1 [l]; 115.9 [i]; 120.3 [k]; 126.0 [g]; 126.6 [h]; 140.8 [f]; 152.3 [j]; 173.5 [a].
13C NMR (DMSO-d6, 600 MHz, 298 K): δ (ppm) = 27.6 [e]; 30.3 [b]; 36.5 [c]; 44.5 [d]; 48.0 [p]; 49.6 [mfa]; 50.6 [mmea]; 54.0 [n]; 60.0 [o]; 63.7 [2]; 68.7 [1]; 70.3 [3]; 81.8 [lfa]; 83.1 [lmea]; 109.1 [r]; 110.9 [s]; 115.9 [i]; 119.6 [kfa]; 120.3 [kmea]; 126.0 [g]; 126.6 [h]; 140.8 [f]; 143.1 [t]; 152.3 [j&q]; 173.5 [a].
13C NMR (DMSO-d6, 600 MHz, 298 K): δ (ppm) = 27.5 [e]; 30.3 [b]; 36.5 [c]; 44.5 [d]; 48.0 [p]; 49.6 [mfa]; 50.6 [mmea]; 54.0 [n]; 60.0 [o]; 63.7 [2]; 68.7 [1]; 70.2 [3]; 81.8 [lfa]; 83.1 [lmea]; 109.1 [r]; 110.9 [s]; 115.9 [i]; 119.6 [kfa]; 120.3 [kmea]; 126.0 [g]; 126.6 [h]; 140.8 [f]; 143.1 [t]; 152.3 [j&q]; 173.5 [a].
13C NMR (DMSO-d6, 600 MHz, 298 K): δ (ppm) = 27.5 [e]; 30.3 [b]; 36.5 [c]; 44.5 [d]; 48.0 [p]; 49.6 [mfa]; 50.6 [mmea]; 54.0 [n]; 60.0 [o]; 63.7 [2]; 68.7 [1]; 70.2 [3]; 81.8 [lfa]; 83.1 [lmea]; 109.1 [r]; 110.8 [s]; 116.0 [i]; 119.6 [kfa]; 120.3 [kmea]; 126.2 [g]; 126.8 [h]; 141.1 [f]; 143.1 [t]; 152.3 [j&q]; 173.5 [a].
The structural features of PEG400-DPA and PEG400-DPA-mea were characterized by 1H NMR, 13C NMR, FTIR and elemental analysis (Fig. 1, Fig. S1–3†). The 1H NMR spectrum of PEG400-DPA (Fig. 1a) reveals peaks corresponding to methylene protons [1,2] adjacent to the carbonyl group in β- and α-position (δ = 3.55 and = 4.06 ppm respectively), attesting the successful esterification of PEG400. Furthermore, the characteristic carbonyl peak [a] at δ = 173.5 ppm in 13C NMR (Fig. S1†) and its correlation in 2D NMR with DPA characteristic methylene protons [1,2] confirm the formation of the ester bond. The absence of impurities or by-products peaks suggests that quantitative conversion was nearly reached. From the 1H NMR spectrum of PEG400-DPA-mea (Fig. 1b), the characteristic peaks corresponding to the formation of the benzoxazine rings are revealed at δ = 3.88 and δ = 4.80 ppm, which correspond to Ar–CH2*–N [h] and O–CH2*–N [g], respectively. The experimental integrations of the methylene protons of the oxazine rings are 5.81H and 5.95H, respectively, corresponding to roughly 75% of the closed benzoxazine rings (theoretical value of 8.00H each). The remaining 25% of end-capping is attributed to opened benzoxazine rings labelled with * in Fig. 1b. In such opened structures, the primary amine has reacted with the phenolic group, but the ring is not closed between the –OH and the nitrogen. The non-closed structures can still be involved in the crosslinking process and affect the rate of transesterification reactions similarly to closed structures. The disappearance of the peak at δ = 9.2 ppm suggests that 100% of the phenolic groups reacted, and this is confirmed by elemental analysis as the experimental ratio of carbon and nitrogen atoms C/N is equal to 67/4 (theoretical C/N = 68/4). The wide signal centered at δ = 4.51 ppm is attributed to the aliphatic hydroxyl groups –OH [k] (ex. 3.88H, th 4.00H). In the 13C NMR spectrum (Fig. S2†), the characteristic oxazine ring carbons are found at δ = 50.6 and δ = 83.1 ppm (for Ar–*CH2–N [m] and O–*CH2–N [l], respectively). The formation of PEG400-DPA-mea was also confirmed by FTIR analysis (Fig. S3†). The strong absorption peak at 1730 cm−1 is typical of the ester CO stretching. The presence of the benzoxazine rings, confirmed by the characteristic bands at 1230 and 932 cm−1 (attributed to the C–O–C asymmetric stretching and the C–H out-of-plane vibration in the trisubstituted benzene ring, respectively), and by the decrease of the intensity of the –OH stretching vibration centered at 3339 cm−1. Finally, the peak at 1030 cm−1 corresponds to the absorption of the primary alcohol C–O stretching and –OH in-plane deformation.
DSC measurements revealed that PEG400-DPA and PEG400-DPA-mea have a similar softening temperature (5.6 and 7.2 °C respectively, Fig. S4†). An exothermic peak (Texo,1 = 110–220 °C) was observed only in the case of PEG400-DPA-mea, attributed to the ring-opening polymerization (ROP) of benzoxazine moieties. It is worth indicating the benzoxazine ROP is triggered at a very low temperature compared to traditional benzoxazines, generally in the range of 150–200 °C.59 The apparent low ROP temperature is related to the activating effect of alcohol functionality through hydrogen bonding, as previously reported in the literature.60,61 A second exothermic peak centered around 250 °C (Texo,2) is attributed to a thermal degradation, also confirmed by TGA (Fig. S5†). PEG400-DPA-mea was subjected to a curing treatment monitored by rheology at 140 °C (Fig. 2a). The recorded rheograms present the evolution of the storage modulus (G′) and the loss modulus (G′′) during the polymerization of the monomer. The behavior of PEG400-DPA-mea when heated is typical to thermosets with a significant increase in both G′ and G′′. The approximate gelation (tgel), defined as the crossover point of G′ and G′′, was reached quickly after 145 s of isothermal curing. This high reactivity could be explained by the high functionality of the system. Rheological characterization of polymerized PEG400-DPA-mea, so-called poly(PEG400-DPA-mea), is reported in Fig. 2b. The measurement was done in torsion mode on a bar sample cured in a bar-shape mold as described in the Experimental section (one hour at T = 150 °C). The DSC thermogram of poly(PEG400-DPA-mea) did not reveal an exothermic peak, indicating a complete polymerization (Fig. S6†). The moduli were measured to 0.6 GPa and 10 MPa in the glassy and rubbery states, respectively. The α mechanical relaxation (Tα) was measured at 93 °C according to the maximum of the tanδ. The significant broad tan delta is characteristic of networks constituted of a wide distribution of chemical structures, assigned to the transesterification reactions occurring during the curing. The Tg of poly(PEG400-DPA-mea) was also measured by dilatometry (Fig. S7†). The transition was measured at the onset of the inflection (79 °C) and is more representative of the service temperature of the vitrimer than the Tα. It is worth indicating that the low thermal expansion associated to the Tg is consistent with the near-zero volumetric expansion characteristic of polybenzoxazines.24
Fig. 2 (a) Isothermal rheology monitoring of PEG400-DPA-mea at 140 °C (b) Rheology temperature sweep curves in torsion mode of poly(PEG400-DPA-mea). |
(5) |
Fig. 3 (a) Stress relaxation curves of poly(PEG400-DPA-mea) at different temperatures and (b) Arrhenius plot obtained from stress relaxation experiment of poly(PEG400-DPA-mea). |
The linear fitting of ln (τ*) versus 1/T plot (correlation coefficient of 0.991) suggests that the network follows an Arrhenius-like flow characteristic. The activation energy (Ea) of transesterification reactions was obtained from the slope of the Arrhenius equation and yielded 115 kJ mol−1 (Fig. S7;† the detail of the calculation is reported in the ESI†). The theoretical Tv was found at 88 °C for poly(PEG400-DPA-mea), in the range of the vitrimers developed by Leibler et al. for epoxy/acid systems.5,6 In the present work, the catalytic effect originates from the neighboring group participation (NGP) of the NR3 groups in the mechanism of the TER (Scheme 1), in a similar fashion than described by Du Prez et al. in a recent review.11 The activation of the –OH groups is promoted by intramolecular hydrogen bonding with the lone electron pair carried by the nitrogen atoms. While the energy of the H–O bonds decreased owing to the N–H interaction, the atom of oxygen became nucleophilic enough to attack the electrophilic center of the carbonyl bond, allowing the TER to occur.
Network | Type of internal catalysis | 103*νca (mol cm)−3 | N/COOb | OH/COOd | T g (°C) | T α (°C) | E a KJ mol−1) | τ*i (S) [T] | Ref. | |
---|---|---|---|---|---|---|---|---|---|---|
a Determined from the Flory Rehner equation (2). b Number of NR3 functionalities per ester bonds (*confirmed by elemental analysis). c From the literature. d Number of –OH per ester bonds (* determined from 1H NMR). e Determined by dilatometry experiment. f Determined by DSC experiment. g Measured from the maximum peak of tanδ curve. h Extrapolated from the Arrhenius equation. i Determined by stress relaxation experiment. | ||||||||||
Epoxy resin | Excess of –COOH groups/β-hydroxy ester | — | — | 1–2c | — | 8 | 104 | ∼104 [150 °C] | 18 | |
Poly(hydroxyethylmethacrylate) | β-Keto ester | 2.4 ± 0.3c | — | 1.5c | — | 130 | 111 | ∼1000 [150 °C] | 21 | |
Epoxy resin | Excess of –OH groups | — | — | >8c | 63f | 70 | 63 | ∼4500 [180 °C] | 19 | |
Epoxy resin | Excess of –OH groups | — | — | 0.625c | — | 57 | 64 | ∼5000 [180 °C] | 20 | |
Epoxy resin | Covalently bonded NR3 groups | — | 0.027 c | 0.9c | — | 69 | 94 | ∼ 1000 [160 °C] | 16 | |
Epoxy resin | Covalently bonded NR3 groups/β-hydroxy ester | — | 0.5 c | 1c | −1f | 22 | — | >104 [170 °C] | 17 | |
Epoxy resin | Covalently bonded NR3 groups/excess of –OH groups | — | <0.1c | 1c | 120 f | 135 | 125 | >104 [170 °C] | 22 | |
Polybenzoxazine | Poly(PEG200-DPA-mea) | Covalently bonded NR3 groups/excess of –OH groups | 81 ± 5 | 2 | 1.67* | 125 | — | 106 | 814 [150 °C] | This work |
Poly(PEG400-DPA-mea) | 24 ± 1 | 2* | 1.95* | 79 | 93 | 115 | 422 [150 °C] | |||
Poly(PEG400-DPA-mea75/fa25) | 69 ± 1 | 2 | 1.38* | 113 | — | 126 | 2012 [150 °C] | |||
Poly(PEG400-DPA-mea50/fa50) | 118 ± 17 | 2 | 0.91* | 121 | — | 131 | 3172 [150 °C] | |||
Poly(PEG400-DPA-mea25/fa75) | 117 ± 19 | 2 | 0.50* | 125 | — | 136 | 3410 [150 °C] | |||
Poly(PEG2000-DPA-mea) | 1.5 ± 0.1 | 2 | 1.93* | — | −34 | 154 | 36 [150 °C] |
The effect of the structural features of the benzoxazine-based vitrimer was investigated by tuning the crosslinking density of the material and the number of –OH groups. The effect of the crosslinking density was assessed by preparing two materials with a PEG of molecular weight of either 200 or 2000 g mol−1. In these materials, the ratio NR3/ester/–OH groups (N/COO/OH) was similar (2/1/2), but the concentration of the dynamic exchangeable sites was decreasing along with the molecular weight of the PEG. Once polymerized, these materials were annotated as poly(PEG200-DPA-mea) and poly(PEG2000-DPA-mea) for the sake of clarity (Table 1, rows 8 and 13). The effect of the number of –OH groups was investigated by preparing three additional materials, where a part of mono-ethanolamine was substituted by furfurylamine (fa). They were called poly(PEG-DPA-mea75/fa25), poly(PEG-DPA-mea50/fa50), poly(PEG-DPA-mea25/fa75), corresponding to materials where 75%, 50% and 25% of mea was substituted by 75%, 50% and 25% of fa, respectively. NMR revealed that they correspond to materials containing a ratio of N/COO/OH equal to 2/1/1.38, 2/1/0.91 or 2/1/0.5, in respect to the order given in the sentence above (Table 1, rows 10–12). The details of the preparation and characterization of all the materials can be found in the ESI (Fig. S8–14 and S18–25†).
As expected, the crosslinking density was decreasing when the PEG molecular weight was increasing, reaching (81 ± 5) × 103 mol cm−3, (24 ± 1) × 103 mol cm−3 and (1.5 ± 0.1) × 103 mol cm−3 for poly(PEG200-DPA-mea), poly(PEG400-DPA-mea) and poly(PEG2000-DPA-mea) respectively. The crosslinking density of poly(PEG400-DPA-meax/fa100−x) were found to be similar to poly(PEG200-DPA-mea), close to 100 × 103 mol cm−3. They are higher than νc of (polyPEG400-DPA-mea) in reason of the involvement of the furan ring in the network formation.30,41,59
According to the stress relaxation curves, all these materials behaved like vitrimers (Tables S2–3, Fig. S15–17 and S26–29†). Their Ea and τ* at 150 °C were determined from isothermal relaxation measurements (Table 1, column 8 and 9) and plotted in Fig. 4a and Fig. 4b as a function of their νc. A clear dependence of the Ea on the number of –OH groups is depicted on Fig. 4a (values encircled by a dashed line). Despite their similar crosslinking density, the Ea of poly(PEG-DPA-mea75/fa25), poly(PEG-DPA-mea50/fa50), and poly(PEG-DPA-mea25/fa75) are increasing while the amount of –OH groups is decreasing (Ea = 126, 131, 136 kJ mol−1 respectively). In the case of poly(PEG2000-DPA-mea), which crosslinking density is the lowest, Ea reached the value of 156 kJ mol−1. In the more crosslinked network (poly(PEG200-DPA-mea)), Ea decreased to 106 kJ mol−1. Lowering the concentration of –OH groups, either by decreasing the νc or the total amount of –OH groups leads to an increase of the Ea. These experiments confirm that the energy needed to activate the dynamic exchanges is clearly governed both by the excess of –OH groups and the concentration of dynamic sites in the network. It is worth indicating the Ea related to the relaxation of theses PBZs vitrimer are in the same range than other reported vitrimers catalyzed either by external or internal tertiary amine.5,6,16,22 However it cannot be excluded that aromatic –OH groups may also be involved in the transesterification mechanism and contribute to the high value of Ea. Indeed, the transesterification with phenoxy is well documented.64–66 Nevertheless, it is worthy to mention that even after a couple of hours at 170 °C, the relaxation of PEG400-DPA-fa, i.e. in the absence of aliphatic –OH was not observed. The results do not exclude the possible involvement of the phenoxy groups in the exchanges, but it is not observed in the conditions of the experiments described here.
Fig. 4 Evolution of τ*150 °C and Ea as a function of the crosslinking density of the different polybenzoxazine vitrimer. |
The evolution of τ* follows another trend (Fig. 4b). A clear dependence exists with the concentration of –OH groups, as attested by the significant increase of τ* when decreasing the amount of –OH groups for materials of similar νc (poly(PEG400-DPA-meax/fa100−x)). τ* remains reasonable (lower than 1 hour at 150 °C) even for the material displaying the lower amount of –OH groups (Table 1, row 12). However, despite their lowest concentration of dynamic sites, the fastest behaviors were reached for the materials with the lowest νc (Table 1, rows 9 and 13). This trend indicates that the speed of the dynamic exchange is also driven by the mobility of the chains.62,63
The very short τ* compared to similar catalyst-free vitrimers can be explained by the abundant number of NR3 groups (coming from the benzoxazine ROP). Indeed, the polymerization of PEGn-DPA-meax/fa100−x follows a ROP, which leads to the formation of a network with an abundant number of tertiary amines, significantly higher in comparison to the previously reported catalyst-free vitrimers (Table 1, column 4). Therefore, the nucleophile substitution of the ester bonds by the –OH groups is highly promoted. This behavior is in adequation with one of the first observations made by Leibler et al. about the relationship between the amount of catalyst and the short τ* of vitrimers.6 Moreover, the catalytic effect is more pronounced thanks to the close position of the NR3 groups regarding the –OH groups, in agreement with the NGP theory recently disclosed by Du Prez et al.11 and illustrated in Scheme 1.
Fig. 5 (a) Self-healing behavior of poly(PEG400-DPA-mea) (b) Life cycle of the bio-based polybenzoxazine vitrimer by reshaping, reprocessing and recycling. |
Fig. 6 Storage modulus of poly(PEG400-DPA-mea) determined in tensile and single cantilever mode after successive recycling (one, two and five times respectively). |
The self-healing, recycling, reshaping, and reprocessing of poly(PEG400-DPA-mea) without any loss of properties were successfully demonstrated. Therefore, this research reflects the suitability of polybenzoxazines to design easily synthesizable mono-component, catalyst-free, and fast responsive vitrimers.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/d1py00324k |
This journal is © The Royal Society of Chemistry 2021 |