Imine based covalent adaptable networks from diacetone acrylamide polymerization

doi:10.21203/rs.3.rs-5264717/v1

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Imine based covalent adaptable networks from diacetone acrylamide polymerization

https://doi.org/10.21203/rs.3.rs-5264717/v1

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The construction of covalent adaptable networks (CANs) without the need for post-modification, complex monomer synthesis routes, or expensive materials is highly desirable for the practical application of dynamic covalent chemistry. In the present study, the commercially available acrylate monomer, diacetone acrylamide (DAAM), was initially polymerized using a traditional radical polymerization method. Subsequently, it was cross-linked with amine agents under hot-processing conditions to form aliphatic imine-based CANs. The resulting materials exhibited glass transition temperatures (T_g) in the range of 95 to 107°C, good thermal stability, mechanical and thermomechanical properties. All samples were amenable to mechanical recycling. Post-recycling, both the tensile strength and Young's Modulus exhibited a slight deterioration, retaining approximately 80% of their original properties. The results from gel content analysis and structural characterization of both pristine and recycled samples indicate that the observed reduction in mechanical properties and T_g (approximately 70°C) can be attributed to a decrease in the degree of cross-linking and the release of aliphatic ketone groups. Furthermore, all samples demonstrated degradability under acidic conditions, attributable to their aliphatic imine structure. By using this facile approach to prepare acrylate-based imine CANs, we establish an important framework for polymer materials that are both reprocessable and biodegradable.

imine bond

dynamic covalent networks

acrylate monomer

reprocessability

acid degradation

Thermoset resin, a type of polymer with covalent bonding, shows excellent resistance toward solvent and chemical degradation. Due to the cross-linked structure in the thermosetting resins, hot-processing and recycling are impossible, thus these materials cannot meet the environmental-friendly requirements. Recently, the covalent adaptable networks (CANs) have been designed into cross-linking polymers, endowing their recycling, shape reconfiguration and self-healing properties[1–3].

CANs are cross-linked polymers where the polymer chains as well as cross-linking points are reversible and allow network rearrangement under external stimuli, such as heat[4, 5] and pH[6]. Derived by the bond exchange mechanism, CANs are divided into two groups[6]. The equilibrium of bond breakage and reformation endow the polymer flowing in the dissociative CANs. The network would undergo a state with reduced even completely depolymerized connectivity. Representative examples

of dynamic chemistries in dissociative CANs include Diels-Alder reaction[7, 8], oxime-urethane exchange[9, 10], disulfide radical exchange[11], hindered urea[12], thiocarbonate exchange [13]and so for. By comparison, associative CANs are dynamic polymer networks which are rely on the thermo-activated bond exchange reactions to facilitate networks rearrangement. During this stage, bond formation process occurs prior to bond breaking, thus resulting the conservation of cross-link density and network integrity[14]. Many associative crosslinking chemistries for CANs have been developed, such as the most important transesterification[15–17], transamination of vinylogous urethane[18, 19], trans(thio)esterification[20], silyl ether exchange[21], olefin metathesis[22], imine exchange[23, 24], and more.

Imine bond, a classically reversible covalent bond, is formed by the condensation reaction between aldehydes and amines[25–27]. Three routes have been reported regarding the reversible mechanism as for imine: Hydrolysis, amine-imine exchange, and imine metathesis[28]. Until now, this strategy has been a simple and important approach to construct imine based vitrimers[23, 29, 30]. Our group has reported the polySchiff vitrimers form vanilline based dialdehyde monomer, subsequently, the commercial terephthalaldehyde was also emerged to construct the imine based vitrimers[25, 27]. For example, the repairable woven carbon fiber composites with full recyclability were enabled by malleable polyimine networks as reported by Zhang et al[31]. As for Epoxy vitrimers based on imine chemistry, numerous vanilline based epoxys and hardeners with imine bonding were introduced into CANs[32, 33]. Ye et al has reported vanillin-based degradable epoxy vitrimers though the synthesis of vanilline based epoxy monomer[26]. Similarly, recyclable and malleable epoxy thermoset bearing aromatic imine bonds was designed by Abu-Omar et al[24]. As for the novel hardeners, the synthesis of imine-containing hardeners from vanilline and commercial amine has also been performed[34, 35].

With the exploration of CANs, the introduction of dynamic covalent bonds into commercial plastics and acrylate materials has attracted increasing attention in recent years[36, 37]. For example, the polySchiff structure is synthesized by condensation of the aldehyde groups from two vanillin methacrylate units with the amine groups [38–40]. Similarly, methacrylates possessing disulfide bonds are introduced into the copolymerization of methacrylates to yield the crosslinked materials[39, 41–44]. Furthermore, poly(acrylate) containing pyridine side groups could be cross-linked by diiodo molecules via pyridine-iodo quaternization[45]. Boronic esters based CANs are constructed by introducing the phenylboronic acid group into acrylate monomer[16, 46]. Besides, vinylogous urea vitrimers are simply afford by the radical copolymerization of (2-acetoacetoxy)ethyl methacrylate that are then converted into vitrimers in a single step by treatment with a trifunctional amine[47, 48].

Diacetone acrylamide (DAAM) is a commercially available, non-toxic monomer that contains a ketone group, making it a promising candidate for reactions with amine cross-linkers to produce polyimine vitrimers. Although DAAM has been previously reported for the synthesis of pH-sensitive and self-healing hydrogels[49–51], limited research has focused on its application as a hot-reprocessable vitrimer. Inspired by these studies, we aimed to introduce imine bonds into CANs using the commercial DAAM monomer without any post-modification. Herein, we describe the synthesis of aliphatic imine vitrimers and their reprocessing ability, mechanical properties and acid degradability.

Materials

Diacetone acrylamide (DAAM, ≥ 99%), Diethylenetriamine (DETA, ≥ 98%) and dibenzoyl peroxide were purchased from Aladdin Company.

Polymer Synthesis and Characterization

In our study, we targeted PDAAM vitrimers, which are acrylate polymers with CAN structures that can be tuned through the cross-linking degree. Typically, in order to prepare PDAAM homopolymer, DAAM (100mmol) was dissolved in acetonitrile solvent and its weight percent was fixed to 30wt%. The weight ratio of the initiator to the monomer was adjusted to 0.5%. After charging with nitrogen for 30 minutes, the polymerization reaction was started at 80 ^oC for 2 hours. Precipitates from this crude product were filtered and dried for two hours at 100°C after being precipitated into large amounts of water to remove the residual monomer. The monomer conversion was around 82.4%.

Further cross-linking of the above prepared PDAAM was achieved using diamine, whose content was varied to tune the cross-linking degree. After dissolving predetermined amount of PDAAM in solvent for a while at 80°C, a specific molar ratio of amine agent (DETA) was added into the above solution as a final step. Because of the quick reaction between aliphatic amine with keton group of DAAM, a gelling state was observed once they were mixed together. This gel was oven-dried at 100 ^oC for about 12 h and then grinded with mechanical pulverizer to get powder. Then, the solid was hot processed at 120 ^oC at 12MPa for 15min to get a flat film which was recorded as PDAAM-DETA. The molar ration of DETA to DAAM was ranged from 10%, 20% and 30%, referred as PDAAM-DETA, PDAAM-2DETA and PDAAM-3DETA, respectively.

Characterization

Fourier transform infrared (FTIR) spectra were recorded on a Nicolet 560 FTIR spectrometer. The powder samples were characterized using the KBr pellet technique. With respect to the films, they were directly measured by the ATR model. Each spectrum was recorded with 32 scans in the frequency range of 4000–400 cm^− 1 with a resolution of 2 cm^− 1. CDCl₃ was used as the solvent to record nuclear magnetic resonance (NMR) spectra on a Bruker 400 (400 MHz) spectrometer. The thermal properties of polyimine film were performed on a differential scanning calorimeter (DSC) (NETZSCH, DSC 214). The sample was dried in a vacuum oven at 100°C for 3 h before conducting experiments. The temperature was gradually increased from 0°C to 200°C at 10°C/min. All the above-mentioned temperature controls were performed under nitrogen atmosphere (60 mL/min flow rate). The thermal stability of the films was measured by thermal gravimetric analysis (TGA; TA instrument, model TGA55) at a heating rate of 10°C/min from 30°C to 600°C under nitrogen atmosphere (50 mL/min flow rate). Dynamic mechanical analysis (DMA) was performed on a DMA 7100 instrument using single-beam mode at 1 Hz with a heating rate of 3°C/min in air atmosphere. The mechanical properties of the polyimine cross-linked films were measured on a 5567 Universal Testing machine with a 1 kN sensor. The gauge length was 50 mm, and the test was performed at a 10 mm/min cross-head speed. The average thickness values of the films with 4mm width were calculated with a micrometer over five measurements. At least five species were tested for each sample. The solvent resistance was investigated by immersing 0.1g vitrimers in pure water, acid water, EtOH, THF, DMSO, DMF, and acetonitrile (ACN) for 24 hours at 60°C. Swelling ratio (SR) and gel fraction (GF), where m0 is the initial mass, m₁ is the final mass after drying, and m₂ is the swelling mass after residual solvent on swelling samples was wiped off. GF was calculated by m₁/m₀ and SR was obtained from m₂/m₁. The degradation properties were assessed by immersing 0.1g vitrimers into HCl solution (pH = 1 and 7) and a mixture of DMF and 0.1 M HCl at 60°C for 24 hours. A reprocessing test was performed on a hot-pressing machine. The films were cut into small pieces with scissors, placed into a round steel mold (10 cm diameter and 0.5 mm thickness), and reprocessed at 120°C for 15 min at 12 MPa. After cooling to room temperature, the recycled films were obtained and stress − strain tests were performed as previously described.

Synthesis and characterization of PDAAM

The traditional radical homopolymerization of PDAAM and subsequent reaction with diamine curing agents (DETA) were investigated in this study,. The chemical structure and average molecular weight of the polymer were analyzed using FTIR, NMR, and GPC techniques, respectively. The successful synthesis of PDAAM (see Fig. 1) was confirmed by the disappearance of ethylene absorption peaks, centering at 1622 cm^− 1 (FTIR) and 6.24, 6.19, 6.06, 5.60 ppm (¹H-NMR) after polymerization[52]. GPC analysis revealed a high molecular weight of the polymer (68 KDa). The thermal and mechanical properties of PDAAM were subsequently analyzed using TGA, DSC and DMA. The TGA results indicates that the onset and maximum degradation temperatures of PDAAM are approximately 275°C and 300°C, respectively. The T_g exhibits two distinct platforms, suggesting the presence of two types of polymer chain transitions in PDAAM, occurring at approximately 46°C and 80°C (Fig. 2a). These observations can be attributed to the formation of intermolecular hydrogen bonding between the amide bond and amide/aliphatic carbonyl groups. Overall, the elevated T_g values suggest that the material possesses inherently rigid mechanical properties. Based on DMA (Fig. 2b), it is obvious that the sharp tanδ peaks in PDAAM are associated with T_g, which is associated with polymer chain relaxation. There are two tanδ peaks, centering at 63.0 and 95.8°C, which are consistent with the DSC results. With regard to the mechanical properties, the Young’s modulus, tensile strength, and elongation at break were measured to be 0.64 GPa, 10.3 MPa, and 1.14%, respectively as shown in Fig. 2c and 2d.

Structural, thermal and mechanical properties of PDAAM vitrimers

PDAAM based vitrimers were easily synthesized by cross-linking the aliphatic ketone of PDAAM with an amine group of cross-linker. When DETA was added to PDAAM solution (ACN solvent) at 80°C, it only took about one minute for the gelation process, suggesting a rapid imine reaction. As the gel dried in the oven, its color changed from transparent to yellow, suggestive of the further imine reaction during heating step. Besides, during the formation of cross-linking networks, water and solvent are evaporated from the gel, converting it into a rigid foam. After then, this foam was grinded and further hot-processed at 120 ^oC at 12MPa for 15min to get a flat film. As indicated by the FTIR results (Fig. 3), The PDAAM exhibits characteristic stretching vibrations of the amide carbonyl group at 1648 cm^− 1 and the aliphatic carbonyl bond at 1705 cm^− 1, respectively. Additionally, the absorption peak near 1532 cm^− 1 corresponds to the bending vibration of the –N–H bond from both primary and secondary amine groups[52]. Typically, the formation of imine structures is indicated by an absorption peak at 1650 cm^{− 1 [53]}; however, this peak is unfortunately obscured by the amide carbonyl vibrations. Despite this interference, there is a noticeable decrease in the relative peak intensity of the aliphatic carbonyl bond at 1705 cm^− 1, which is decreased with the further imine reaction between it and cross-linking agents. Here, the spectra were first normalized and the peak of –N-H (1564 cm^− 1) was used as an internal peak to assess the relative intensity of aliphatic carbonyl bond, which could be referred as \(\:{R}_{I}={A}_{1705}/{A}_{1564}\). For pure PDAAM, the relative intensity value is 0.29. With the addition of 10% DETA (–NH₂/DAAM=0.2 molar ratio), this value gradually decreases to 0.22, and further declines to 0.17 with 30% DETA (–NH₂/DAAM = 0.6 molar ratio). To confirm the presence of imine-based cross-linking networks, a gel fraction experiment was conducted. After refluxing with THF at 80°C for 12 hours, all PDAAM-DETA vitrimers retained their original shape without disintegrating into smaller particles, with approximately 94.3%, 95.7%, and 96.4% residue remaining for PDAAM-DETA, PDAAM-2DETA, and PDAAM-3DETA, respectively. It is evident that the incorporation of the DETA cross-linker enhances the cross-link density of the polymer network, a conclusion that will be further substantiated by the subsequent DMA results. TG experiments were conducted to assess the thermal stability of PDAAM-based vitrimers. The results indicate that these vitrimers do not decompose until reaching 215°C, as denoted by the Td_5% in Fig. 2b.

Following the formation of vitrimer structures, notable changes in thermal properties were observed. As illustrated in Fig. 4a, the T_g of polyimine films are higher than that of PDAAM (80°C). As the degree of cross-linking increases, T_g of PDAAM-3DETA rises by approximately 10°C. DMA results corroborate this trend, as illustrated in Fig. 4b, showing a gradual increase in T_g associated with the imine reaction. Besides, The weaker tanδ peak indicates that the viscoelasticity of vitrimers is relatively lower with the cross-linking of DETA. The formation of dynamic covalent bonds restricts the relaxation of PDAAM main chains, leading to diminished tanδ peaks. Besides, the tanδ peaks of PDAAM vitrimers are much wider with the rise of cross-linking degree, may be due to the differences in the motion ability of imine chain compared with that of PDAAM backbone. The presence of rubbery plateaus above the T_g temperature confirms that these systems possess cross-linking networks. The rubbery phase modulus for PDAAM-DETA, PDAAM-2DETA and PDAAM-3DETA are 2.41, 18.41 and 34.5 MPa respectively. Crosslinking density of tri-dimensional networks (ν_e) and the average molar mass between two cross-link nodes (M_c) are calculated [54, 55] and summarized in Table 1. Consistent with expectations, ν_e increases from 289 to 1392 mol/m³ with higher DETA content, which correspondingly reduces M_c from 1392 to 289 g/mol.

Table.1 Details of thermal properties and cross-linking parameters for PDAAM based vitrimers

	Td_5% (°C)	T_dmax (°C)	T_g (°C)^a	T_g (°C)^b	ν_e (mol/m³)	M_c (g/mol)
PDAAM-DETA	237.5	358.8	84	95.2	237	1392
PDAAM-2DETA	223.1	337.3	86	95.6	1806	290
PDAAM-3DETA	218.8	336.7	97	107	3292	289

^aDetermined by DSC method; ^bDetermined by DMA method.

The mechanical properties of pristine films were shown in Fig. 4c and 4d. The Young’s Modulus, tensile strength and elongation at break of pristine PDAAM-DETA are 0.73GPa, 15.81MPa and 5.53%, respectively. Compared with pure PDAAM film, the mechanical properties of PDAAM-DETA are obviously improved; furthermore, a significantly increasing trend was observed with the imine reaction processing. Finally, the PADDM-3DETA shows the highest Young’s Modulus and tensile strength, which are highly up to 0.98GPa and 23.2MPa, respectively.

Reprocessing of PDAAM-DETA vitrimers

Like Schiff-based imine CANs [25], the introduced keton-based aliphatic imine enables PDAAM-DETA to be reprocessed. To confirm this feature, the cured polyimine resins were cutted into small pieces and then pressed in a steel mold at 120 ^oC at 12MPa for 15min. As shown in Fig. 5, hot-pressing can reprocess them into new coherent resins, endowing by the imine exchange reaction. The reprocessing was identified three times to check the changes in the mechanical properties, and the results were shown as Fig. 6. Obviously, the tensile strength and Young’s Modulus both show a slightly deterioration, but they are still maintained about 80% of original properties. The similar results have been widely observed in the vitrimers, mainly attributed to the accumulation of defects and thermal aging during hot processing[56].

Based on the structural and thermal characterization of the reprocessed vitrimers, Fig. 7 illustrates the reasons for their decreased mechanical properties. An inspection of the data in Fig. 7a reveals that the release of aliphatic keton groups after reprocessing, which is proved by the increased relative intensity for the peak centering at 1705cm^− 1. This result might be caused by the oxidation of amine groups in the air especially at high processing temperature, which would transform as aminoxyl radical. This deduce could be proved by the oxidation of the aminopropyltriethoxysilane under oxidizing conditions[57]. With the depletion of amine groups, the content of dynamic covalent bonds from aliphatic-based imine decreases, consequently leading to a reduction in the cross-linking degree. These hypothesis is substantiated by the gelling content data (Fig. 8b), which shows a decrease from 94.3–87.3% over three repeated times. The DMA results (Fig. 7b) further corroborate this findings, indicating a decreasing T_g and a broadening of the tanδ peak. These observations suggest the presence of two distinct types of chain movements in the reprocessed PDAAM-DETA: one occurring around 70 ^oC but the other one centered around 95 ^oC. With the side reaction of amine groups during hot-processing, the release of aliphatic keton groups certainly decreases the cross-linking degree of PDAAM-DETA.

Solvent resistance and acid hydrolysis of vitrimers

The solvent resistance was evaluated before the acid degradation, as displayed by Fig. 8a. here, the vitrimers were immersed into pure water, DMSO, DMF, EtOH and ACN at 65°C for 24h. All of vitrimers are easily swelled and without any break. Compared with other solvents, the SR of PDAAM-DETA in DMF is high up to around 500%, indicating the worst of solvent resistance in DMF compared with other solvents. From these results, it could be concluded that DMF are much more suitable than others for the vitrimers degradation because of their excellent swelling ability. Here, The GF, representing the cross-linking degree in the pure solvent, was also carefully investigated. It is shown that the weight loss of vitrimers in the good solvents (ACN) is consistent with the theoretical value (20%), due to the dissolution of PDAAM in CAN. As for other solvents, these value is much higher, indicating that the cross-linking of –C = O with –NH₂ from DETA is an effective approach to impart the dissolution of PDAAM in solvent. Besides, the GF exhibits a good trend with the increase of DETA content (Fig. 8b). When it comes the reprocessed PDAAM-DETA vitrimers, the slightly declined GF in the THF solvent indicates a decreasing cross-linking degree, due to the release of aliphatic ketone groups as suggested by the FTIR results.

The chemical degradation of PDAAM-DETA vitrimers is of importance for attractive plastic replacements. Usually, polyimine can be chemically degraded through the reversible imine bond under acid condition. Hence, PDAAM-DETA were immersed in the mixed hydrochloric acid/DMF solution and then its residual weight percentages were recorded. Because of the insoluble property of PDAAM in the water, theoretically, the residuals of vitrimers should be pure PDAAM without any DETA, thus the weight percentage of PDAAM in PDAAM-DETA vitrimers was calculated to be 94.2% and this value is in reasonable agreement with actual samples, as displayed in Fig. 9. Obviously, the degradation behaviors are controlled by the acid and polymer swelling. Compared with the pure water, the degradation percentage in acid condition is slightly higher. With the swelling of DMF, the degradation behavior is further processed and the weight loss percentage is much closer with the theoretical value.

In the present study, the aliphatic imine-based covalent adaptable networks (CANs) was designed by the reaction between poly(diacetone acrylamide) (PDAAM) and diethylenetriamine (DETA) under hot-processing conditions. The obtained PDAAM-DETA vitrimers exhibited glass transition temperatures (T_g) in the range of 95 to 107°C. Their Young’s Modulus and tensile strength, which are highly up to 0.98GPa and 23.2MPa, respectively. Approximately 80% of the original properties remained after hot reprocessing, including tensile strength and Young's modulus. The results from gel content analysis and structural characterization of both pristine and recycled samples indicate that the observed reduction in mechanical properties and T_g (approximately 70°C) can be attributed to a decrease in the degree of cross-linking and the release of aliphatic ketone groups. Furthermore, all samples demonstrated degradability under acidic conditions, attributable to their aliphatic imine structure. By using this facile approach to prepare acrylate-based imine CANs, we establish an important framework for polymer materials that are both reprocessable and biodegradable.

Covalent adaptable networks CANs

Diacetone acrylamide DAAM

Diethylenetriamine DETA

Glass transition temperatures T_g

Fourier transform infrared spectroscopy FTIR

Differential scanning calorimeter DSC

Nuclear magnetic resonance spectroscopy NMR

Thermal gravimetric analysis TGA

Dynamic mechanical analysis DMA

Swelling ratio SR

Gelling fraction GF

Crosslinking density ν_e

Average molar mass between two cross-link nodes M_c

Conflicts of interest

There are no conflicts to declare.

Author Contribution

All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by [Hanghang Chen], [Zihao Hou] ,[Liqiong Li], [Haoyu Deng], [Yixue Ouyang]and [Xiancai Jiang]. The first draft of the manuscript was written by [Dezhan Ye] and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

Acknowledgements

This work was supported by the foundation of National Natural Science Foundation of China (Grant No. 52203015)

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Imine based covalent adaptable networks from diacetone acrylamide polymerization

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Abstract

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Introduction

Experimental

Materials

Polymer Synthesis and Characterization

Characterization

Results and discussion

Synthesis and characterization of PDAAM

Structural, thermal and mechanical properties of PDAAM vitrimers

Reprocessing of PDAAM-DETA vitrimers

Solvent resistance and acid hydrolysis of vitrimers

Conclusion

Abbreviations

Declarations

Conflicts of interest

Author Contribution

Acknowledgements

References

Additional Declarations

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Version 1