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Synthesis and properties of novel degradable polyglycolide-based polyurethanes

  • Jing-Jing Wang , Ying-Guo Zhou , Qian-Qian Zhang and Jun Zou EMAIL logo
Published/Copyright: May 11, 2024
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e-Polymers
From the journal e-Polymers Volume 24 Issue 1

Graphical abstract

Polyglycolide-based polyurethane was synthesized via chain extension reaction. As the hard segment content increases, its thermal stability and mechanical properties are improved; and the weight loss rate in PBS solution is reduced.

Abstract

Novel degradable polyglycolide-based polyurethanes (PGAUs) were synthesized using polyglycolic diol (PGA diol) as soft segment, 1,6-n-hexane diisocyanate (HDI) as hard segment, and 1,4-butanediol (BDO) as chain extender agent. PGA diol (M n = 10,000 g·mol−1) was obtained by ring-opening polymerization of glycolide in the presence of BDO using stannous octanoate (Sn(Oct)2) as a catalyst. The structures of PGA diol and PGAUs were characterized by Fourier transform infrared (FTIR) and proton nuclear magnetic resonance (1H NMR). The PGA diol and PGAUs were further studied by the means of differential scanning calorimetry, thermogravimetric analysis, tensile testing, scanning electron microscope, and hydrolytic degradation behavior testing. FTIR and 1H NMR analyses indicated that the PGAUs were easily prepared by chain-extension reaction. The results showed that the PGAUs had improved thermal stability and enhanced mechanical properties with the hard segment increased. Degradation behavior suggested that the PGAUs could be degraded in phosphate-buffered saline solution.

Keywords: polyglycolide-based polyurethane; hard segment content; thermal properties; mechanical behavior; hydrolytic degradation

1 Introduction

Polyurethane (PU) has been widely used in biological, electronic, automotive, packaging, and other fields due to its excellent mechanical properties (1,2), processability (3), biodegradability (4), and biocompatibility and corrosion resistance to chemical substances (5,6,7). PU was known to be a kind of complex compound, and many factors of PU such as physical crosslinking, chain structure, cohesion and hydrogen bond, PU elastomer affect corrosion resistance, high wear resistance, and good blood histocompatibility, were widely investigated. For example, Min et al. (8) prepared a biodegradable multiblock PU with 1,6-n-hexane diisocyanate (HDI), polylactide, and poly(glycolide-co-caprolactone). The obtained material had good shape memory and mechanical properties and can be used to fabricate other new materials by altering its composition. Wang et al. (9) synthesized PU using polycaprolactone (PCL) and MDI. They investigated the effects of diisocyanate and oligomer diol (NCO/OH) with different mole ratios on the mechanical properties of the obtained PU. Yang et al. (10) designed and synthesized an amorphous and transparent PU elastomer with excellent self-reinforcing, self-toughening, and self-healing properties. Gao et al. (11) improved the crystallinity of the PU elastomers by reducing the initial orientation and increasing the ultimate tensile strength, resulting in high mechanical properties, high strain, and fast healing.

PU has often been classified into polyether and polyester types according to the different types of polyols (12,13). Polylactic acid (PLA) and PCL-based PUs are two kinds of the most common polyester polyols types (14,15,16,17,18). Degradability is often the focus of research for such materials. As a representative, Takagi et al. (19) synthesized PLA-based PLA–PCL alternating multiblock copolymers by copolymerization of PLA with PCL-diol followed by chain extension reaction in HDI. Liu et al. (20) using polycarbonate ether diol, IPDI and butane-1, 4-diol as raw materials, biodegradable polycarbonate ether polyurethane was prepared as a pressure sensor to reduce the use of fossil materials and reduce pollution. Chen et al. (21) used hydroxyl-terminated polylactic as a hard segment to synthesize PU, which has good hydrophilicity and biocompatibility. It was found that the molecular weight of HO-PLA-OH determined the degradation rate of the PLA-based PU. However, the degradation rate was low, and the mechanical properties of the material were somewhat bad. Polyglycolic acid (PGA), also known as polyglycolic, is the simplest semicrystalline aliphatic polyester, which can be easily thought of as another candidate for biodegradable polyester polyols, resulting from its structural similarity to PLA.

PGA stands out for its impressive mechanical properties (22,23), biodegradability (24,25), biocompatibility, and high crystallinity, making it widely used in biomedicine. PGA-based polyurethanes (PGAUs) are absorbable or soluble in the human body environment, finding applications in bone fixation pins, screws, interference screws for anterior cruciate ligament reconstruction, suture anchors for joint reconnection, etc. As PGAUs undergo molecular weight reduction, accompanied by structural changes, their strength and stiffness diminish, allowing gradual load transfer to repair tissue, thereby mitigating pressure shielding and osteopenia, and facilitating in situ absorption without requiring secondary surgical removal (26,27,28,29).

Additionally, the development of numerous bioelastomers has emerged, crucial for tissue engineering scaffold materials due to the significant impact of elastic properties on cell function and tissue development. However, traditional bio-based materials like PLA, PGA, and poly(lactic-co-glycolic acid) possess limitations such as high strength, a maximum elongation at break of less than 20% during plastic deformation under stress, and an uncontrollable degradation rate, thereby constraining their application in the biomedical field. Si et al. (30) showcased a method to enhance PLA’s mechanical properties by incorporating PU through dynamic vulcanization, demonstrating the potential for chemical copolymerization to tailor molecular structures to meet the performance criteria of bio-based PU.

In this study, a series of new type of PGAUs was synthesized by the common two-step polymerization with glycolide (GA) and HDI as raw material and 14-butanediol (BDO) as initiator and chain extender. The reactive route and the chemical structures of the PGAUs were characterized by proton nuclear magnetic resonance (1H NMR) spectroscopy and Fourier transform infrared (FTIR) spectra analysis. The influence of hard segment content (C hs) on the thermal properties, mechanical properties, and degradation behavior was investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), tensile testing, scanning electron microscope (SEM), and hydrolytic degradation behavior testing, respectively. Furthermore, the newly synthesized PGA diol and PGAUs were immersed in a solution of sodium phosphate buffer (PBS buffer) for 15 days, respectively, and the effect of C hs on their degradation behaviors was studied by FTIR and SEM.

2 Materials and methods

2.1 Materials

BDO (AR grade) and methanol (AR grade) were purchased from Sino Pacific group chemical reagent Co., Ltd, and used without further purification. HDI (AR grade) was bought from Sigma-Aldrich were used without further purification. Purified ethyl lactide (GA) was obtained from Shanghai Pujing Chemical Technology Co., Ltd. Stannous octanoate (Sn(Oct)2) from Sigma-Aldrich was used without further purification. Toluene (AR grade) was purchased from China National Pharmaceutical Group Chemical Reagent Co., Ltd.

2.2 Preparation of PGA diol and PGAUs

Dihydroxyl-terminated PGA (PGA diol) with regulated molecular weight was synthesized via ring-opening polymerization of GA in the presence of BDO using Sn(Oct)2 as a catalyst. The procedure was as follows: 150.0 g (1.3 mol) GA, 1.35 g (0.015 mol) BDO, and 0.012 g (0.008 wt%) Sn(Oct)2 were put into a 500 mL three-neck round-bottom flask equipped with mechanical stirrer. The polymerization was first carried out at 160℃ and 3,000 Pa for 2 h and then continued at 180℃ and 100 Pa for another 3 h. The resulting polymer was purified by dissolving in chloroform and precipitating in excessive methanol. The white powder product was dried to constant weight in vacuum oven at 60℃.

The chain-extension reaction was performed in bulk using a glass reactor filled with nitrogen. PGA diol was put into the reactor which was vacuumed and purged with nitrogen three times. Then, the reactor was immersed in a 160℃ silicone oil bath. The reactants were stirred with a mechanical stirrer when they were completely molten, and then the predetermined amount of HDI was injected into the reactor. The chain extension reaction was finished in 1 h. The resulting polymer was also purified using the same procedures as PGA diol to remove any potential cross-linked product.

2.3 Characterization

2.3.1 FTIR spectroscopy

FTIR was recorded using a Digilab FTS 2000 FTIR instrument in the wavelength range of 4,000–500 cm−1. The specimens were milled into powders and then mixed and laminated with KBr. The resolution and scanning time was 4 cm−1 and 32 times, respectively.

2.3.2 NMR spectroscopy

The 1H NMR spectrometer (1H NMR) used an AVANCE III Fourier transform NMR spectrometer from Bruker, Switzerland. The operating frequency was 400 MHz, deuterated TFA as the solvent, and tetramethylsilane as the internal standard.

2.3.3 DSC measurements

DSC analysis was carried out using the DSC 8000 (PerkinElmer). PGA diol and PGAU thin sheets weighted 3–5 mg were placed in the crucible and sealed. The test was protected with nitrogen atmosphere, and the test procedure was as follows: the temperature increased from −70 to 250℃ at a rate of 10℃·min−1, and the insulation lasted for 3 min. Then, the temperature was cooled to −70℃ at a rate of 30℃·min−1 and the temperature was maintained for 3 min. Finally, the second heat flow curve was obtained by increasing from −70℃ to 250℃ at a rate of 10℃·min−1. The DSC curves were further processed to analyze the glass transition temperature (T g), cold crystallization temperature (T cc), and melting temperature (T m) of the samples.

2.3.4 TGA

The TGA was also used to know the thermal behavior of the obtained PGA diol and the PGAUs and was carried out using a Pyris Diamond TGA from PE company. The flow rate of N2 was 30 mL·min−1, the temperature increased from 25℃ to 600℃, and the heating rate was 10℃·min−1.

2.3.5 Mechanical properties

Tensile test samples were fabricated using PGA diol and PGAUs powder obtained according to the ASTM-D638 standard. The tensile rate was 10 mm·min−1, and stress–strain behaviors were recorded and further analyzed.

2.3.6 SEM

The microstructure of PGA diol and PGAUs powder samples was characterized by Merlin Compact SEM of Carl Zeiss, Germany. The accelerating voltage was 20 kV and the sample surface was sprayed with gold (31,32).

2.3.7 Hydrolytic degradation studies

For degradation behavior testing, the obtained PGA diol and PGAUs were hot pressed into flakes and immersed in a solution of phosphate buffer (pH = 7.2, 25℃) for 0, 3, 6, 9, 12, and 15 days. At the end of the degradation test, the samples were washed three times with deionized water, weighed, and dried, and the weight loss rate was calculated.

3 Results and discussion

3.1 Synthesis of PGA diol and PGAUs

As shown in Scheme 1, PGA diol was prepared by ring-opening polymerization of GA under the catalysis of Sn(Oct)2 and in the presence of initiator BDO. PGAUs were synthesized by end-capping the PGA diol with HDI, followed by a reaction in toluene with chain extender BDO. Only one kind of PGA diol (M n = 10,000 g·mol−1) was obtained because the main interest of the paper was to characterize the PGAUs and examine the influence of the hard segments on the mechanical properties, especially on the thermal properties and degradation behaviors.

Scheme 1 The synthesis route of PGA diol and PGAUs.
Scheme 1

The synthesis route of PGA diol and PGAUs.

According to the molar ratios of PLA:HDI:BDO in the reaction feed, the PUs were divided into four groups, i.e. PGAU-23%, PGAU-28%, PGAU-32%, PGAU-36%, meaning PGA:HDI:BDO = 0.09:1.09:1, 0.07:1.07:1, 0.06:1:06:1, and 0.04:1.04:1, respectively. The theoretical molecular weight of the PGAU is applicable to Eq. 1.

(1) M n ,cal = 90 + [ GA/alcohol (mol/mol) in the feed ] × 116

The basic data for the PGAUs are listed in Table 1. Their solubility in chloroform decreased with increasing hard segment content.

Table 1

Feed ratios of the PGAUs with different hard segment contents

Samples Hard segment content (wt%) PGA:HDI:BDO (mol) Theoretical molecular weight (g·mol−1)
PGAU-23% 23 0.09:1.09:1 12,125
PGAU-28% 28 0.07:1.07:1 13,854
PGAU-32% 32 0.06:1.06:1 14,468
PGAU-36% 36 0.04:1.04:1 16,618

3.2 Characterization of PGA diol and PGAUs

Figure 1 shows FTIR spectra of PGA diol, HDI, and PGAUs. It can be seen from Figure 1 that the peak of 3,511, 1,744, and 2,960 cm−1 appeared in the infrared spectra of the hydroxyl-terminated polyglycolide (PGA). These three characteristic absorption peaks were attributed to the stretching vibration of the –OH bond, C═O bond, and –C–H bond, respectively. All of these characteristic peaks belonged to PGA diol characteristic peaks, which were consistent with the literature review and proved the success of PGA polymerization on hydroxyl-terminated oligomers (33). In terms of the HDI infrared spectra, the peak of 2,249 cm−1 belonged to the vibration absorption peak of the isocyanate (−NCO). Furthermore, in the PGAUs infrared spectrum, the characteristic absorption peak at 3,322 and 1,540 cm−1 belonged to the –N–H stretching vibration peak and the bending vibration peak of the PU, respectively. The characteristic absorption peak of 1,683 and 1,746 cm−1 corresponded to the carbonyl group (–C═O) and the ester carbonyl group (–C═O) of carbamate in polyester, respectively. Compared to the PGA diol and HDI infrared spectrogram shown in Figure 1a, the peak of 3,500 cm−1 in hydroxyl characteristic absorption peak decreased, and the peak of 2,274 cm−1 in the isocyanate characteristic peak also disappeared. In addition, 1,540 and 3,322 cm−1 of the characteristic –N–H absorption peak appeared, suggesting that the isocyanate in the system completely reacted with the hydroxyl group. It can be concluded that PGAUs were successfully polymerized (34). Furthermore, with increasing C hs, the characteristic absorption peak of carbonyl (–C═O) changed from a single peak to a sharp peak and finally to a double peak, as shown in Figure 1b, indicating that the content of the carbonyl group gradually increases. The high- and low-wave number carbonyl peaks belonged to ester carbonyl of PGA diol and ester carbonyl of carbamate, respectively. In conclusion, PGAU polymerization with different C hs was shown to be successful.

Figure 1 FTIR spectra of PGA diol, HDI, and PGAUs. (a) PGA diol, HDI, and PGAUs. (b) PGA diol and PGAUs with different hard segment contents.
Figure 1

FTIR spectra of PGA diol, HDI, and PGAUs. (a) PGA diol, HDI, and PGAUs. (b) PGA diol and PGAUs with different hard segment contents.

Figure 2 shows the 1H NMR spectra of the PGA diol and PGAUs with different C hs. In Figure 2a, the characteristic peak of 11.50 and 4.02 ppm is the solvent CF3COOD and the residual H2O of the PGA diol, respectively. The characteristic peak of 5.14 ppm corresponds to the methylene in the repeating unit –O–CH2–CO (a). The chemical shift of –CH2–CO (b), which is interrelated with the hydroxyl terminus, is 4.60 ppm (35). The initiator used in the synthesis of the prepolymer PGA diol is BDO, and its corresponding chemical displacement of –OCH2 (c) is 4.25 ppm, which moved to the lower field due to the ester bond. The characteristic peak of 2.08 ppm is the intermediate –CH2 (d) characteristic peak of BDO. It can be concluded that the hydroxyl-terminated PGA is synthesized successfully.

Figure 2 1H NMR spectra of PGA diol and PGAUs with different hard segment contents: (a) PGA diol (b) PGAU-23% (c) PGAU-28% (d) PGAU-32% (e) PGAU-36%.
Figure 2

1H NMR spectra of PGA diol and PGAUs with different hard segment contents: (a) PGA diol (b) PGAU-23% (c) PGAU-28% (d) PGAU-32% (e) PGAU-36%.

Figure 2(b)–(e) shows 1H NMR spectra of PGAUs with C hs of 23–36%. In comparison to PGA diol, the number of characteristic peak of almost all PGAUs is obviously higher. Take PGAU-23% as an example, and the result is shown in Figure 2b. The characteristic peak at 5.06 and 4.64 ppm is the methylene O–CH2–O (a) of the hard segment and methylene O–CH2–O (b) of the terminal hydroxyl, respectively. The characteristic peak at 4.28 ppm is the methylene (–O–CH2) (c) connected to the ester group of the initiator BDO, and the characteristic peak at 1.62 ppm is the chemical displacement of methylene –CH2 (d) in the middle of the BDO. The characteristic peak at 4.42–4.64 ppm and 1.44–1.62 ppm is the chemical shift of methylene (–COO–CH2) (e) and –COO–CH2–CH2 (f) of chain extender BDO, respectively. The corresponding chemical displacement of –OCN–CH2 (g) and –NH–CH2 (h) is 3.31 and 4.96 ppm, respectively. Furthermore, the chemical shifts of –NH–CH2–CH2 (i), –ONC–CH2–CH2 (j), and –OCN–CH2–CH2 (k) range from 1.44 to 1.62 ppm. It can also be found that the characteristic peak of NH is not apparent, caused by the extremely active and low hydrogen atom of the carbamate group (NHCOO–), located in 8.18 ppm.

In addition, the difference of the above Figure 2(b)–(f) is that the proton peak of –NHCOO moved in high field gradually with the increase of C hs, and the integral area of the corresponding proton peak of –NHCOO was varied. It can be concluded from the 1H NMR spectrum shown in Figure 2 that the PGAUs is successfully synthesized, which is consistent with the results of the infrared spectral analysis.

3.3 Thermal properties

Figure 3 shows the DSC heating scan of PGA diol and PGAUs in the second heating run. It could be found that the curves of PGA diol and PGAUs exhibit only one glass transition, in addition, we can see that the melting peak of the PGAUs is significantly smaller than that of PGA diol, the specific details are presented in the Figure 3. On the one hand, only one glass transition temperature means that the PGA diol soft segments and hard segments are miscible in the PGAUs. On the other hand, this is because the molecular weight of PGA diol is small (M n = 10,000 g·mol−1). When it becomes the soft segment of the PGAUs, their crystallization ability is significantly reduced compared to that of PGA diol because of the restraint from the hard segments. The PGA diol chains are covalently linked with the hard segments, and this restraint is understandable.

Figure 3 DSC curves of PGA diol and PGAUs: (a) secondary heating (b) first heating.
Figure 3

DSC curves of PGA diol and PGAUs: (a) secondary heating (b) first heating.

It is interesting to notice that the T g values of all PGAUs (22.71–40.02℃) are lower than that of the PGA diol (43.41℃), which could be ascribed to the multi-segmental structure of the PGAUs. The hard segment domain has much lower T g compared with the soft domain, at temperatures near T g of the PGA diol chains, the hard segments are in the glassy state and provide obstacles to the movements of the PGA diol chains. Therefore, T g of the PGA diol phase is lower than that of the free PGA diol and increases with increasing hard-segment content, as shown in Table 2. However, among the four different hard segment of the PGAUs, the T g decreases as the addition of HDI increases, probably due to the flexibility of the HDI units.

Table 2

The T g of PGA diol and PGAUs with different hard segment contents

Samples PGA diol PGAU-23% PGAU-28% PGAU-32% PGAU-36%
T g (℃) 43.41 40.02 29.61 28.58 22.71
∆H m (J·g−1) 85.2 31.30 29.71 30.85 32.94

It can be observed from the first heating curve in Figure 3 that the appearance of the melting double peaks (b and e) is attributed to the absence of microphase separation in PGAUs. At this stage, the short hard segment sequences dispersed within the PGA phase exhibit high dispersion. Consequently, some hard segment molecular chains facilitate the formation of hydrogen bonds and promote the crystallization of PGA molecular chains, while others impede the rearrangement of PGA molecular chains. This increased molecular chain randomness consequently lowers the melting point, resulting in the manifestation of double melting peaks.

The crystalline changes of PGAUs can be inferred indirectly through the melting enthalpy values presented in Table 2, which reflect changes in crystallinity with increasing hard segment content. PGA diol demonstrates the highest melting enthalpy, indicating strong molecular chain crystallization ability, while PGAUs exhibit lower crystallization ability due to the addition of HDI/BDO disrupting the orderly arrangement of molecular chains. Moreover, increasing hard segment content leads to higher ΔH m values, suggesting enhanced microphase separation and increased crystallinity in PGAUs.

Figure 4 shows the thermogravimetric curves of PGA diol and PGAUs with different C hs. It can be seen from Figure 4a that PGA diol has only one nitrogen degradation process, and the thermal degradation temperature of PGA diol is 354℃, which was consistent with the literature (36). It has been known that PGA diol could be decomposed into glycolic acid, cyclic oligomer, and carboxylic acid in the thermal degradation process, and the carboxylic acid would accelerate the thermal degradation process of PGA diol.

Figure 4 Thermogravimetric diagrams of PGA diol and PGAUs: (a) TGA, (b) enlarged TGA, and (c) DTG diagram.
Figure 4

Thermogravimetric diagrams of PGA diol and PGAUs: (a) TGA, (b) enlarged TGA, and (c) DTG diagram.

Compared to the PGA diol, the thermal stability of the PGAUs with different C hs is generally lower, as can be found in Figure 4. The PGAUs with the C hs of 23–36% usually experience three stages of thermal degradation. In the first stage, the degradation occurs between 190 and 200℃, which can be attributed to the degradation of small molecular substances remaining in PU and the polyurea group generated by side reactions. The maximum degradation temperatures in the first stages of the PGAUs with the C hs of 23–36% are 191℃, 195℃, 199℃, and 199℃, respectively, as shown in Figure 4c. The hydrogen bond density between minor molecules gradually increases with the increase of C hs, which causes the volatilization of small molecules and leads to a gradual increase in the degradation temperature. The second stage of degradation temperature is realized to be 320–337℃. In this temperature range, the hard carbamate section of the PGAUs cracks, and the heat resistance of carbamate is lower than that of the ester group, and the hard section was preferentially decomposed. In the hard segment degradation process, the carbamate bond, which is connected with the chain extender BDO, first undergoes thermal decomposition, and the products are N═C═O and BDO. The pyrolysis of isocyanate (N═C═O) then turns into carbonized diimine and CO2. After that, carbamate groups that attached to hydroxyl groups at the GA end are degraded, and the decomposed products are isocyanate and hydroxyl-terminated GA (37). The third stage of degradation is located at 450–455℃, which is mainly attributed to the fracture of the ester bond in the hard segment. When the temperature rises to 450℃, PGAUs undergoes thermal decomposition, and the products of the decomposition of BDO are THF and water vapor. In addition, it can be seen from Figure 4c that the degradation rate in the second stage is higher than that in the other two stages. It may be attributed to the break of the bond between different groups. In the second stage of the degradation, the breaking occurs mainly between isocyanate and polyol macromolecular groups, and the degradation activation energy is relatively low, resulting in a high degradation rate.

The thermal resistance of PGAUs is observed to increase with higher C hs levels. As shown in Figure 4(b) and (c), the thermal resistance follows the order of PGAU-36% > 32% > 28% > 23%. This increase in C hs may lead to a higher intermolecular hydrogen bond density within PGAUs, potentially enhancing their thermal resistance.

3.4 Tensile properties

Figure 5 shows the tensile properties of the PGAUs with different C hs. Among them, a, b, c, d, and e are PGA, PGAU-23%, PGAU-28%, PGAU-32%, and PGAU-36%, respectively. With increasing C hs, the tensile strength increases and the elongation at break gradually decreases. This trend is expected (38,39,40,41,42,43). It can be seen from Figure 5a that PGA is a brittle fracture, and when PGA is used as a soft segment of PU, stress yield occurs in the b, c, d, and e curves. When the hard segment content of PGAUs is 36, 32, 28, and 23 wt%, the elongation at break is 136.58%, 217.78%, 332.16%, and 440.63%, respectively. It can be seen that the elongation at break of PGAU-23% The rate is 3.23 times that of PGAU-36%. The decrease in elongation at break is due to the increase in the hard segment content and the decrease in the soft segment content in the system. The soft segment content affects the elastic properties of PGAUs. The increase of the tensile strength can be attributed to the hydrogen bond between carbamate in the hard crystal region, which plays the role of physical crosslinking, increasing the intermolecular force and improving the tensile strength. Compared to other PGAUs, the tensile strength of PGAU-23% is lower, only 2.20 MPa, suggesting that PGAU-23% has no significant improvement in its mechanical properties, which was consistent with Katsuhiko’s work (44).

Figure 5 Tensile properties of PGA diol and PGAUs: (a) the stress–strain curves and (b) the tensile strength and elongation curves.
Figure 5

Tensile properties of PGA diol and PGAUs: (a) the stress–strain curves and (b) the tensile strength and elongation curves.

As can be seen in Figure 5b, with the increase of C hs, the tensile strength of PGAU-36% is 1.97 times that of PGAU-23%. The hydrogen bonds in PGAUs exist mainly in the hard segment region, which is formed by HDI/BDO. The number of hydrogen bonds in the hard segment gradually increases, which leads to an increase of effective physical crosslinking, resulting in a high tensile strength.

The elastic property of the PGAUs is mainly related to the soft segment, so when the C hs increases, the soft segment content of the PGAUs decreases and the elongation at break gradually decreases. Therefore, with increasing C hs, the elongation at break of the PGAUs gradually decreases.

3.5 Degradation of PGA diol and PGAUs

It is well known that phosphate-buffered saline solution is frequently used to evaluate the biodegradability of the materials because it is similar to the internal environment, the osmotic pressure, and the ion concentration of the body. For example, the PH value of the phosphate-buffered saline solution is close to the internal environment of the body.

Figure 6 shows the degradation of the PGAUs with different C hs in phosphate-buffered saline solution at 37℃. The weight loss rate gradually decreases as the C hs in the PGAUs increases from 23% to 36%. This is because the hydrolysis of the PGAUs is mainly the hydrolysis of the ester group in the hard segment. The existence of a hard segment promotes the crystallization of the PGAUs molecules, which is not conducive to the formation of the void and reduces the permeability of water vapor, and the ester group hydrolysis. As a result, the weightlessness rate of the PGAUs suddenly decreases with increasing C hs. It can also be seen from Figure 6 that soaking time also has a substantial impact on the PGAUs weight loss, and weight loss increases with increasing degradation time. It is no exception, and the autocatalysis of carboxylic acid can promote the hydrolysis of the ester group, resulting in the increase in the hydrolysis rate.

Figure 6 The weight loss curves of PGA diol and PGAUs.
Figure 6

The weight loss curves of PGA diol and PGAUs.

In addition, PGAU-28% is selected as a representative and its structural changes in the degradation process are investigated by FTIR spectra, as shown in Figure 7. Figure 7a shows that the characteristic peak position of the degraded PGA diol has only a slight shift, compared to the original characteristic peak of the PGA diol, indicating that it is difficult to change the structure of the PGA diol during the degradation cycle of the experiment. With increasing degradation time, the strength of the characteristic absorption peak of the carbonyl group gradually decreases, and the peak gradually flattens out, indicating that the PGA diol component has been hydrolyzed. Compared to PGA diol, the carbonyl peak area of PGAU-28% decreases significantly with increasing degradation time, as shown in Figure 7b. This may be because the ester carbonyl group of PGAU-28% breaks and eventually forms small molecules of glycolic acid, resulting in the reduction in the strength of the carbonyl group during degradation. Furthermore, almost all other characteristic functional groups of the PGAU-28% are not obviously changed, suggesting that the PGAU-28% and PGA diol have similar structural changes in the degradation experiment.

Figure 7 FTIR spectra of PGA diol and PGAU-28% before and after degradation in (a) PBS PGA diol and (b) PGAU-28%.
Figure 7

FTIR spectra of PGA diol and PGAU-28% before and after degradation in (a) PBS PGA diol and (b) PGAU-28%.

The surfaces of the original and degraded PGAUs with different C hs are compared by SEM, as shown in Figure 8. It can be seen from Figure 8a that the PGA diol surface is relatively smooth and layered. After 15 days of degradation, as shown in Figure 8d, some irregular parts and small holes are found on the surface of the PGA diol, indicating that the PGA diol has been degraded. Compared to PGA diol, PGAUs had more severe surface peeling due to degradation, and the surface roughness of the sample gradually increases. With increasing C hs, a large number of gullies and cracks form on the sample surface, as shown in Figure 8e, f, j, k, and l. Therefore, the PGAUs provided more sites for water molecules with an increase in C hs, causing an accelerated hydrolysis rate.

Figure 8 Scanning electron micrographs of PGA diol and PGAUs with different hard segment content degradation for 15 days. (a) PGA/0 Day, (b) PGAU-23%/0 Day, (c) PGAU-28%/0 Day, (d) PGA/15 Days, (e) PGAU-23%/15 Days, (f) PGAU-28%/15 Days, (g) PGAU-32%/0 Day, (h) PGAU-36%/0 Day, (i) PGAU-32%/15 Days, and (j) PGAU-36%/15 Days. The scale bar in (a) is shared by all pictures.
Figure 8

Scanning electron micrographs of PGA diol and PGAUs with different hard segment content degradation for 15 days. (a) PGA/0 Day, (b) PGAU-23%/0 Day, (c) PGAU-28%/0 Day, (d) PGA/15 Days, (e) PGAU-23%/15 Days, (f) PGAU-28%/15 Days, (g) PGAU-32%/0 Day, (h) PGAU-36%/0 Day, (i) PGAU-32%/15 Days, and (j) PGAU-36%/15 Days. The scale bar in (a) is shared by all pictures.

4 Conclusion

A series of novel PGA-based PUs with PGA as soft segments and HDI as hard segment have been successfully synthesized by chain-extension reaction of PGA diol using HDI as a chain extender. The chemical structure of PGA diol and PGA-based PUs was confirmed by the means of FTIR and 1H NMR. The results proved that the chain-extension reaction was a very effective method to synthesize PGA-based PUs. The DSC results for the PGAUs showed only one T g, which proved that the hard and soft segments were completely miscible in the PGAUs. TGA and hydrolytic degradation studies showed that with the increase of hard segments, the PGAUs had improved thermal stability and enhanced mechanical properties, while the weight loss rate decreased in phosphate-buffered saline solution. Therefore, they can meet different practical demands through changing the hard segments and adjusting the ratio of hard to soft segments.

Acknowledgment

The authors would like to express their gratitude to the National Natural Science Foundation of Jiangsu Province (No. BK20210894) for their financial support.

  1. Funding information: This study was supported by the National Natural Science Foundation of Jiangsu Province (No. BK20210894).

  2. Author contributions: J.J. Wang: writing – original draft; Y.G. Zhou: funding acquisition, methodology; Q.Q. Zhang: investigation; J. Zou: conceptualization, data curation, supervision.

  3. Conflict of interest: On behalf of all authors, the corresponding author states that there is no conflict of interest.

  4. Data availability statement: All data included in this study are available upon request by contact with the corresponding author.

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Received: 2024-01-24
Revised: 2024-03-28
Accepted: 2024-03-29
Published Online: 2024-05-11

© 2024 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/epoly-2024-0014
Keywords for this article
polyglycolide-based polyurethane; hard segment content; thermal properties; mechanical behavior; hydrolytic degradation
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BY 4.0

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