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Exploring a new method for high-performance TPSiV preparation through innovative Si–H/Pt curing system in VSR/TPU blends

  • Shujuan Shi , Haipeng Cui , Hongchi Tian EMAIL logo , Shijia Zhang and Yanfang Zhao EMAIL logo
Published/Copyright: December 24, 2024
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e-Polymers
From the journal e-Polymers Volume 24 Issue 1

Abstract

This article explores the positive impact of a homemade polyurethane block copolymer (PDMS-PU) compatibilizer on silicone rubber/polyurethane (VSR/TPU) systems. A novel method for preparing silicone thermoplastic vulcanizate (TPSiV) materials is introduced, using a hydrogenated silicone oil/platinum (Si–H/Pt) catalytic vulcanization system. This involves high-temperature premixing of VSR, Si–H, and TPU, followed by adding diallyl maleate (DAM) inhibitor and Pt catalyst during the cold roller stage. This method prevents premature cross-linking and ensures thorough mixing and interaction between VSR and TPU. The TPSiV material produced demonstrates high tensile strength (TS, 6.5 MPa), exceptional elongation at break (EB, 500%), good shape stability, stable viscosity under high temperature and shear conditions, excellent low-temperature resistance, and superior damping properties. This innovative preparation method offers significant insights and practical guidance for developing high-performance thermoplastic vulcanizates.

Keywords: silicone rubber; polyurethane; diallyl maleate; vulcanization system, microstructure; high-performance

1 Introduction

Silicone rubber (VSR) has been commercialized in automobiles and medical devices due to its outstanding softness, biocompatibility, non-toxicity, low temperature resistance, and chemical resistance. Its biggest disadvantage is its poor mechanical strength and oil resistance (1,2,3). Thermoplastic polyurethane (TPU) is a lightweight and environmentally friendly thermoplastic elastomer material with excellent tensile strength, flexibility, tissue compatibility, and other properties. It is widely used in the fields of footwear and biological tissue materials (4,5), but its heat aging resistance is poor (6,7,8). Silicone thermoplastic vulcanizate (TPSiV) prepared by dynamic vulcanization (DV) technology is unique in that highly cross-linked VSR is evenly dispersed in the continuous phase of TPU, forming a typical “Sea-island” structure. This structure significantly enhances the performance of simple physical blending of VSR and TPU, especially the elastic and mechanical properties, allowing TPSiV to achieve a substantial improvement in material properties. TPSiV can not only use the same molding processes as traditional plastics, such as injection molding, extrusion, blow molding, and calendering but also has the ability to be processed repeatedly. TPSiV prepared from VSR and TPU through the vulcanization process, because it combines the excellent properties of VSR and TPU, is widely used in the field of wearable devices with stringent material performance requirements, including but not limited to smart bracelets (9), smart glasses (10), and VR Equipment (10), etc.

In the past, the preparation of TPSiV mainly relied on peroxide vulcanization systems (11). Although this process is simple and easy to implement, it has significant limitations. Specifically, the cross-linking rate of VSR under a peroxide system is difficult to accurately control, because the reaction is too fast, which can easily lead to a process out of control (12). More importantly, the free radicals generated by the decomposition of peroxide under high temperature conditions not only promote the cross-linking reaction of methyl/vinyl in VSR, but may also interact with the isocyanate group in the TPU hard segment, taking away the isocyanate group on it, of hydrogen atoms, thereby generating macromolecular free radicals (9). This process severely damages the internal structure of TPU, hinders the phase inversion phenomenon, and results in poor overall performance of the final product.

Currently, using hydrogen-containing silicone oil (Si–H) complex as the vulcanization system and combining VSR and TPU to prepare TPSiV has become a hot topic in the research field. The system has attracted much attention mainly due to its unique vulcanization mechanism: under the catalytic action of Pt catalyst, the vinyl group in VSR undergoes an addition reaction with the –Si–H bond in hydrogen-containing silicone oil, achieving only selective cross-linking of VSR without affecting the structure of TPU. However, this vulcanization system also faces significant challenges: the Pt catalyst exhibits extremely high activity, and once mixed with VSR and Si–H at room temperature, it will quickly trigger the addition reaction, resulting in the subsequent dynamic vulcanization process. The cross-linking degree of VSR is difficult to reach the expected level. This problem directly affects the phase structure construction of TPSiV, thereby weakening its overall performance.

This work first studied the compatibilization effect of a self-made compatibilizer PDMS-PU (containing polysiloxane segments of polyurethane block copolymers) on simple VSR/TPU blends, solving the problem of difficult compatibilization of the system. Based on this study, the Si–H/Pt vulcanization system was used to study and compare the effects of the new method on the microphase structure and properties of TPSiV, in order to provide guidance for the future industrial production of TPSiV.

2 Experiment

2.1 Materials

VSR (110-2) is provided by Zhonglan Chen Guang Chemical Research Institute (Chengdu, China). TPU (B85A11U) is obtained from Bayer Chemicals (Germany). Both Si-H(L202) and Pt (VM-23) are purchased from Jian Cheng Silicone Company (Zhejiang, China). DAM (AK401879) is obtained from Hansi Chemical Company (Shanghai, China). Laboratory-made compatibilizer PDMS-PU is mainly synthesized from polyethylene glycol (PEG), polydimethylsiloxane (PDMS), 4,4′-diphenylmethane diisocyanate (MDI), and 1,4-butanediol (BDI). The molecular weight of PDMS-PU is characterized by gel permeation chromatography (GPC), which has the number average molecular weight (M n) of 5.1 × 103 and the mass average molecular weight (M w) of 4.9 × 104. Other auxiliaries are sold on the market.

2.2 Sample preparation

2.2.1 Preparation of VSR (60 phr)/TPU (40 phr) TPSiV

VSR/TPU/PDMS-PU, etc., are placed to HAKKE (180°C and rotating speed 100 rpm), and fully mixed to torque balance. The simple blends (SB) of VSR/TPU with dosages of 0, 4, 8, and 12 phr PDMS-PU are prepared. Curing agents are not added in this process. The purpose of preparing SB samples is to determine the optimum dosage of compatibilizer PDMS-PU.

VSR (60 phr)/TPU (40 phr) TPSiV samples are prepared using the following new methods and three other traditional methods. In Method 1, VSR/Pt/Si-H are mixed evenly on cold roller, then with TPU, etc., by DV at HAKKE to torque balance. In Method 2, VSR/DAM/Pt/Si-H are mixed evenly on cold roller, then with TPU, etc., by DV at HAKKE to torque balance. In method 3, VSR/TPU, etc., are premixed at HAKKE high temperature and then Pt/Si-H are added to HAKKE by DV to torque balance. In the New method, VSR/Si-H/TPU, etc., are premixed at HAKKE high temperature, then DAM/Pt are added to the above mixture’s surface on cold roller, and finally they are obtained at HAKKE by DV to torque balance. HAKKE’s temperature and speed are 180°C and 100 rpm, respectively, and the dosage of PDMS-PU is 4 phr in all preparation methods.

2.3 Performance and characterization

2.3.1 Morphology studies

The morphology of the samples is examined by using a peak force tapping atomic force microscopy (PF-AFM) (Multimode 8, Bruker Corporation, Germany) because of its high resolution. Before the observation, the samples are polished by using a cryo-ultramicrotome. The distribution of the rubber particle size was determined with the Image-Pro Plus 4.0 software. The number average particle size (d n), weight average particle size (d w), and polydispersity index (PDI) of the VSR phase can be calculated by the following formula:

(1) d n = ∑ i n i d n i ∑ i n i

(2) d w = ∑ i n i d n i 4 ∑ i n i d i

(3) PDI = d w d n

where d ni is the average value of the particle diameters and n i is the number of d ni .

2.3.2 Mechanical performance

The tensile properties of the samples are tested with a tensile machine (Al-7000sl, high-speed rail testing, China) according to ASTM D412 at a tensile rate of 500 mm·min−1. The hardness of the samples is tested with a hardness tester.

2.3.3 Elasticity performance

The tensile recovery properties of the samples are measured using a tensile machine (Al-7000sl, high-speed rail testing, China) by strain recovery test. Strain recovery tests are first extended to 50% elongation, and then the tensile force is zero; the residual strain is defined as the tensile permanent set. The hysteresis loss at 50% elongation is calculated by subtracting the area under the force-retraction curve from the area under the stress–strain curve. The compression set of the samples is tested at room temperature.

2.3.4 Rheological properties

The rheological characterization of samples is investigated using a capillary rheometer (Rosand RH2000, British Malvern Panalytical) at 200°C under the single-bore experiment mode and a shear rate range from 20 to 1,000 s−1. The L/D ratio of the capillary is 16/1 and 0, respectively. Each flow curve is a result from data collected at eight different shear rates during the experiment.

2.3.5 X-ray diffractometer (XRD) analysis

The crystallization behavior of the samples is characterized by XRD (RINT2000 vertical, Japanese Science), with Cu-Kα radiation generated at 40 kV and 100 mA. The wide-angle X-ray diffraction patterns are recorded in the reflection mode at a scanning rate of 0.02°/s from 2θ 5°–90°.

2.3.6 Dynamic mechanical analysis (DMA)

DMA is carried out with a Dynamic mechanical analyzer (VA3000, France 01Db-Metravib) with a tension mode. Dynamic storage modulus (E′) and loss tangent (Tan δ) are determined at a frequency of 1 Hz and a heating rate of 5°C·min−1 from −80 to 100°C.

2.3.7 Rubber process analysis (RPA)

The cured rubber particles in TPSiV with a high degree of cross-linking can be approximately regarded as fillers in the TPU matrix. Thus, the change in the VSR network in the TPU phase can be reflected by the “Payne effect” of VSR/TPU, which is analyzed by a rubber process analyzer (RPA 2000, Alpha, USA). The strain scan conditions were 180°C, 1 Hz, and a strain range of 1–100%. Before the analysis, the samples are preheated for 10 min.

3 Results and discussion

3.1 Study on determining the optimum dosage of compatibilizer PDMS-PU

Compatibilization technology plays a significant role in optimizing the internal structure of composite materials. It can effectively reduce the interfacial tension, improve the bonding strength of the interfacial interface, promote the uniform dispersion of the phases during the blending process, and effectively prevent the aggregation of the dispersed phase, thereby stabilizing the phase structure of the composite material (13). Figure 1 shows the AFM phase diagram of VSR/TPU samples with different PDMS-PU dosages. The phase distribution is intuitively distinguished by different colors in the figure: the pink area represents the TPU phase (continuous phase) with higher adhesion, while the blue area corresponds to the VSR phase (dispersed phase) with lower adhesion. From Figure 1, it can be clearly seen that in the sample without the addition of compatibilizer, the VSR phase has a large particle size and uneven distribution, which reflects the large interfacial tension between the phases and the poor dispersion effect. With the gradual increase in the amount of PDMS-PU, the particle size of the VSR phase first shows a decreasing trend, and then reaches the optimal dispersion state at a certain dosage (such as 4 phr), and the particle size distribution is relatively uniform. The compatibilization mechanism is based on the good compatibility of PDMS segments with VSR and the compatibility of PU segments with TPU. This dual compatibility promotes the close bonding of the phase interface. However, when the amount of PDMS-PU is further increased, the particle size of the VSR phase increases and the distribution becomes uneven again. This may be due to the negative effects caused by excessive compatibilizer, such as enhanced phase separation tendency (14).

Figure 1 AFM phase morphology images of VSR/TPU SB samples with different dosages of PDMS-PU: (a) 0 phr PDMS-PU. (b) 4 phr PDMS-PU. (c) 8 phr PDMS-PU. (d) 12 phr PDMS-PU.
Figure 1

AFM phase morphology images of VSR/TPU SB samples with different dosages of PDMS-PU: (a) 0 phr PDMS-PU. (b) 4 phr PDMS-PU. (c) 8 phr PDMS-PU. (d) 12 phr PDMS-PU.

The statistical results of the particle size and distribution of the VSR phase in SB samples with different PDMS-PU dosages are shown in Table 1. We analyzed the number average particle size (d n), weight average particle size (d w), minimum particle size (d min), maximum particle size (d max), and PDI of the VSR phase in detail. PDI is an important indicator for measuring the uniformity of the particle size distribution of the VSR phase (15). The smaller the value, the more uniform the particle size distribution. It can be clearly seen from the data in Table 1 that with the gradual increase in the dosage of PDMS-PU, d n, d w, and PDI all show a trend of first decreasing and then increasing. Specifically, when the dosage of PDMS-PU is 4 phr, the d n and d w of the VSR phase in the SB sample reach the minimum value, and the PDI is also the lowest, which fully demonstrates that at this dosage, the particle size of the VSR phase is not only the smallest, but also the most uniformly distributed. However, when the dosage of PDMS-PU continues to increase, the particle size of the VSR phase begins to gradually increase, and the particle size distribution becomes more and more uneven. In summary, it can be concluded that 4 phr of PDMS-PU is the key to achieve the best compatibilization effect of VSR/TPU blend system. This discovery not only provides an important basis for optimizing the performance of composite materials, but also points out the direction for subsequent related research.

Table 1

Particle size and distribution of VSR phase with different PDMS-PU dosage

PDMS-PU (phr) d n (μm) d w (μm) d min (μm) d max (μm) PDI
0 1.21 3.72 0.30 1.96 3.07
4 0.48 0.22 0.17 0.91 0.46
8 0.55 0.29 0.18 0.92 0.53
12 0.79 2.76 0.12 1.73 3.49

3.2 Effect of the new method on torque during TPSiV preparation

Based on the above compatibilization studies and Si–H/Pt vulcanization systems, we have improved the method for preparing VSR/TPU TPSiV. The differences between the new method for preparing VSR/TPU TPSiV and other traditional methods are shown in Table 2. The effect of the new method on HAKKE torque during preparation of VSR/TPU TPSiV is shown in Figure 2. According to Table 2 and Figure 2, the torque of Method 1 hardly rises, indicating that VSR is not vulcanized at high temperatures and VSR has been prematurely vulcanized at room temperature. Compared with Method 1, the torque of Method 2 rises immediately without scorching period (M–N), indicating that DAM has a significant inhibition effect on VSR vulcanization at room temperature but no inhibition effect at high temperature. The mechanism of action of DAM is that it forms a new stable complex with the Pt atom of the catalyst through the coordination bond at room temperature to inhibit the addition reaction of VSR/Si–H, and the new complex immediately decomposes at high temperature so that Pt can catalyze the vulcanization of VSR normally.

Table 2

Differences between the new method for preparing TPSiV and other methods

Preparation methods DAM (phr) Process differences
Method 1 0 First VSR/Pt/Si–H is mixed in cold roller and then with TPU, etc., by DV at HAKKE
Method 2 0.5 First VSR/Pt/DAM/Si–H is mixed in cold roller and then with TPU, etc., by DV at HAKKE
Method 3 0 First VSR/TPU, etc., are premixed at HAKKE high temperature and then Pt/Si–H are added to HAKKE by DV
New method 0.5 First VSR/Si–H/TPU, etc., are premixed at HAKKE high temperature, then DAM/Pt are added to the above mixture in cold roller, finally by DV at HAKKE
Figure 2 Effect of the new method on HAKKE (180°C, 100 rpm) torque during preparation of VSR/TPU TPSiV.
Figure 2

Effect of the new method on HAKKE (180°C, 100 rpm) torque during preparation of VSR/TPU TPSiV.

The addition of DAM/Pt to the cold roller (A–B) of the new method makes the subsequent curing degree of VSR (C–D) similar to that of Method 2 (M–N), which is much higher than the torque of Method 1. Compared with the curing time (M–N) of Method 2, the high-temperature premixing of VSR/Si–H/TPU (before Point A) of the new method evenly disperses Si–H in VSR/TPU two phases, which extends the subsequent curing stage (C–D) of VSR for 3 min and further reasonably regulates the vulcanization rate of VSR. Compared with the VSR/TPU high-temperature premixing (before Point E) of Method 3, in addition to ensuring that the cross-linking of VSR occurs after VSR/TPU mixing, the new method of VSR/Si–H/TPU high temperature premixing also disperses Si–H uniformly in VSR/TPU two phases to make the subsequent vulcanization of the VSR more uniform.

The vulcanization mechanism of VSR is that under the heating conditions of Pt catalyst, the vinyl group of VSR undergoes an addition reaction with the hydrogen atom of the –Si–H bond of hydrogen containing silicone oil, and the reaction equation is as follows:

3.3 Effect of the New method on the phase morphology of TPSiV

The AFM plane and three-dimensional (3D) phase morphology images of TPSiV are shown in Figure 3. The statistical graphs of the average particle size distribution of the VSR phase of TPSiV are shown in Figure 4. According to Figure 3, the pink region (high adhesion) is the TPU phase, and the blue region (low adhesion) is the VSR phase. A large amount of VSR of sample prepared by Method 1 fuses into a continuous phase with a micron size to form a co-continuous phase structure with a small amount of TPU. The continuous phase of VSR can seriously hinder the flow of TPU and ultimately lead to poor processing properties of the material. A large amount of VSR of TPSiV prepared by Methods 2, 3, and the new method is dispersed in a small amount of TPU continuous phase, with a typical “sea-island” phase structure, but only the VSR phase prepared by the new method is dispersed evenly. According to Figure 4, the average size of VSR phase domain of the new method (5.1 µm) is the smallest and evenly distributed. The fine size and good dispersion of VSR phase can give TPSiV outstanding comprehensive performance.

Figure 3 AFM plane and 3D phase morphology images of TPSiV prepared by different methods: (a) Method 1. (b) Method 2. (c) Method 3. (d) New method. (e) Method 1 (3D). (f) Method 2 (3D). (g) Method 3 (3D). (h) New method (3D).
Figure 3

AFM plane and 3D phase morphology images of TPSiV prepared by different methods: (a) Method 1. (b) Method 2. (c) Method 3. (d) New method. (e) Method 1 (3D). (f) Method 2 (3D). (g) Method 3 (3D). (h) New method (3D).

Figure 4 Statistical graphs of average particle size distribution of VSR of TPSiV prepared by different methods: (a) Method 1. (b) Method 2. (c) Method 3. (d) New method.
Figure 4

Statistical graphs of average particle size distribution of VSR of TPSiV prepared by different methods: (a) Method 1. (b) Method 2. (c) Method 3. (d) New method.

3.4 Effect of the new method on the mechanical properties of TPSiV

The mechanical properties of TPSiV are shown in Table 3. According to Table 3, the mechanical properties of the samples vary greatly. TPSiV prepared by the new method has the highest TS and EB, and its highly cross-linked VSR phase domain has fine size and good dispersion, which gives it excellent mechanical properties. 300% definite elongation stress (ES) can characterize the rigidity of TPSiV. Generally, the hardness of the material increases with the definite elongation stress, and the hardness of the TPSiV prepared by the new method is slightly higher.

Table 3

Mechanical properties of TPSiV

Methods TS/MPa EB/% ES (300%)/MPa Hardness/shore A
Method 1 1.0 103 1.0 36
Method 2 1.7 150 1.5 41
Method 3 3.6 291 3.2 53
New method 6.5 500 4.9 58

3.5 Effect of the new method on the elasticity performance of TPSiV

Both hysteresis loss and permanent deformation are important parameters reflecting the elasticity of TPSiV. The larger their value, the worse the elasticity of TPSiV (16). The tensile recovery curves of TPSiV are shown in Figure 5(a). The tensile permanent deformation and hysteresis loss curves of TPSiV are shown in Figure 5(b). Figure 6 shows the compression permanent deformation of TPSiV. According to Figures 5 and 6, the tensile permanent deformation, hysteresis loss, and compression set of TPSiV prepared by the Method 1 are the largest, indicating that the elasticity is the worst, because the VSR has almost no cross-linking at high temperature. The TPSiV prepared by the new method has the minimum tensile permanent deformation, hysteresis loss, compression permanent deformation, and the best elasticity.

Figure 5 (a) The tensile recovery curves of TPSiV and (b) the tensile permanent deformation and hysteresis loss curves of TPSiV.
Figure 5

(a) The tensile recovery curves of TPSiV and (b) the tensile permanent deformation and hysteresis loss curves of TPSiV.

Figure 6 Compression set of TPSiV.
Figure 6

Compression set of TPSiV.

3.6 Effect of the new method on the rheological performance of TPSiV

The rheological behavior of TPSiV is generally a complex non-ideal rheological behavior (17). The apparent viscosity–shear rate curves for TPSiV are shown in Figure 7. According to Figure 7, TPSiV prepared by different methods all have prominent pseudoplastic fluid properties, and their apparent viscosity decreases with the increase in shear rate. The viscosity of TPSiV prepared by Method 1 is the highest, because the continuous phase of the VSR seriously hinders the flow of TPU. TPSiV prepared by the new method has the lowest viscosity and better fluidity. The smaller the size of the highly cross-linked VSR dispersed phase domain, the better the processing fluidity of TPSiV. The smaller the size of phase domain and the better the dispersion of highly cross-linked VSR, the better the processing fluidity of TPSiV.

Figure 7 The apparent viscosity–shear rate curves of TPSiV.
Figure 7

The apparent viscosity–shear rate curves of TPSiV.

3.7 Effect of the new method on crystallization behavior of TPSiV

The XRD spectrum of the crystallization behaviors of TPSiV are shown in Figure 8. According to Figure 8, pure TPU has a crystal diffraction peak at 2θ = 16° which is mainly formed by a large amount of accumulation in the soft segment of TPU and 2θ = 40° in the range of 2θ = 5°–90°. Pure VSR shows a weaker crystalline diffraction peak at 2θ = 10°. VSR/TPU SB samples with 0phr PDMS-PU and the TPSiV prepared by different methods show weak diffraction peaks at 2θ = 10° and 16°. A large amount of VSR results in a significant decrease in the intensity of the crystal diffraction peak of pure TPU at 2θ = 16.0° and the disappearance of the crystal diffraction peak of pure TPU at 2θ = 40.0°. It may be that the strong interaction between a large number of VSR and TPU influences the crystallization behavior of TPU, which eventually leads to the obvious lower mechanical strength of TPSiV than pure TPU (18). Different preparation methods have almost no effect on the TPSiV crystallization peak intensity, but have different effects on the 2θ of the TPU crystallization peak. Within a certain range, the smaller the 2θ, the smaller the crystallization size of TPSiV, and the better the mechanical properties of the sample. The 2θ of the TPU crystallization peak of TPSiV prepared by the new method is the smallest, indicating that its mechanical properties are the best, which is consistent with the results of the mechanical properties of Table 3.

Figure 8 XRD spectrum of crystallization behavior of TPSiV.
Figure 8

XRD spectrum of crystallization behavior of TPSiV.

3.8 Effect of the new method on dynamic mechanical properties of TPSiV

DMA is carried out with a dynamic mechanical analyzer with a tension mode (19). The characterization results of the dynamic mechanical properties of TPSiV are represented by the storage modulus (E′)–temperature curve and the loss tangent (Tan δ)–temperature curves of TPSiV, as shown in Figure 9. According to Figure 9, E′ of TPSiV prepared by different methods drops sharply at the glass transition temperature T g and E′of the TPSiV prepared by the new method drops the fastest, and then directly enters the high elastic state. The peak of Tan δ of TPSiV corresponds to its T g. Within the range of −80∼100°C, TPSiV has a strong Tan δ peak and a weak Tan δ peak. The Tan δ peak in the range of −40 to −20°C corresponds to the low temperature T g of TPSiV. Different preparation methods have different effects on low temperature T g of TPSiV. The low temperature T g of TPSiV prepared by the new method is the smallest, indicating that the TPSiV has a low crystallization temperature, good low temperature resistance, and good low temperature elasticity. In addition, the new method also greatly increases the Tan δ peak of TPSiV and effectively improves the damping performance of TPSiV.

Figure 9 The storage modulus (E′)–temperature curves and the loss tangent (Tan δ)–temperature curves of TPSiV.
Figure 9

The storage modulus (E′)–temperature curves and the loss tangent (Tan δ)–temperature curves of TPSiV.

3.9 Influence of the new method on the “Payne effect” of TPSiV

The change in the VSR network in the TPU matrix can be reflected by the “Payne effect” of VSR/TPU TPSiV, which is analyzed by RPA. The characterization results of “Payne effect” of TPSiV are shown in Figure 10. The “Payne effect” means that the storage modulus (G′) of the elastomer with a filler gradually decreases with the increase in strain (20). Within a certain range of strain, ΔG′ (G′max – G′min) is used to characterize the strength of the filler network of the elastomer. In TPSiV system, the smaller the ΔG′, the weaker the strength of the rubber particle network and the better the dispersibility of the rubber. In the strain range of 1–100%, except for the Method 1, G′ of the TPSiV prepared by other methods obviously has a tendency to gradually decrease with the increase in the strain and thus has a “Payne effect.” In the strain range of 1–100%, the ΔG′ of TPSiV prepared by the new method is small, indicating that the rubber network structure is weak and the dispersibility of rubber is good in this system, which is consistent with the research results of AFM.

Figure 10 Storage modulus (G′)–strain curves of TPSiV.
Figure 10

Storage modulus (G′)–strain curves of TPSiV.

4 Conclusion

  1. In this study, 4 phr PDMS-PU self-made compatibilizer effectively improves the compatibility of the VSR/TPU two phases. Based on the above research and Si–H/Pt vulcanization system, high performance VSR/TPU TPSiV is successfully prepared by the New method.

  2. The addition of DAM to the cold roll effectively solves the problem of premature crosslinking of VSR during the mixing of VSR/Si–H/Pt at room temperature. The inhibition mechanism is that DAM first forms a coordination bond with the Pt atom of the catalyst at room temperature to form a new stable complex, thereby inhibiting the addition reaction of VSR/Si–H. At high temperatures, the new complex immediately decomposes, allowing Pt to catalyze the sulfurization of VSR normally.

  3. The HAKKE high-temperature premixing of VSR/Si–H/TPU not only makes the cross-linking of VSR occur after VSR/TPU fully mixed but also disperses Si–H evenly in the VSR/TPU two phases, which makes the cross-linking rate and uniformity of VSR reasonably regulated. TPSiV prepared by the new method has a finer phase (5.1 μm of VSR phase domain) and good dispersibility, which gives it outstanding comprehensive performance (TS 6.5 MPa, etc.).

  4. The study of new method has more important guiding significance for the commercialization of TPSiV in the future.

  1. Funding information: This work was supported by the National Key Research and Development Program of China (2022YFD230120201) and Tropical High-efficiency Agricultural Industry Technology System of Hainan University (THAITS-3).

  2. Author contributions: Shujuan Shi: writing – original draft. Haipeng Cui: writing – review and editing. Hongchi Tian: methodology and formal analysis. Shijia Zhang: writing – original draft. Yanfang Zhao: formal analysis, visualization, and project administration.

  3. Conflict of interest: No conflict of interest.

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Received: 2024-08-05
Revised: 2024-11-17
Accepted: 2024-11-21
Published Online: 2024-12-24

© 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-2024-0081
Keywords for this article
silicone rubber; polyurethane; diallyl maleate; vulcanization system, microstructure; high-performance
Creative Commons
BY 4.0

Articles in the same Issue

  1. Research Articles
  2. Flame-retardant thermoelectric responsive coating based on poly(3,4-ethylenedioxythiphene) modified metal–organic frameworks
  3. Highly stretchable, durable, and reversibly thermochromic wrapped yarns induced by Joule heating: With an emphasis on parametric study of elastane drafts
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  11. The effects of property variation on the dripping behaviour of polymers during UL94 test simulated by particle finite element method
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  51. Preparation of hydrophobic silicone rubber composite insulators and the research of anti-aging performance
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  53. Study on hydrophobicity and aging characteristics of epoxy resin modified with nano-MgO
  54. Optimization of baffle’s height in an asymmetric twin-screw extruder using the response surface model
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  56. Experimental investigation on low-velocity impact and compression after impact behaviors of GFRP laminates with steel mesh reinforced
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  58. Investigation of the compaction density of electromagnetic moulding of poly(ether-ketone-ketone) polymer powder
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  69. Recent progress in properties and application of antibacterial food packaging materials based on polyvinyl alcohol
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