TW202102555A - Vitrimer and preparation method thereof - Google Patents

Abstract

The present disclosure provides a method for vitrimer. The method includes following step: performing a synthesizing step and performing a cross-linking curing step. The synthesizing step is for synthesizing the monomethacrylate monomer and glycidyl methacrylate by a polymerization method to obtain a copolymer. The cross-linking curing step is for the copolymer reacting with a bifunctional crosslinking agent under the catalysis of a transesterification catalyst to obtain a vitrimer. Accordingly, the vitrimer of the present disclosure has stronger stress and greater strain than the general thermosetting resin, and has good heat resistance, plasticity and repairability.

Description

Plastic thermosetting resin and preparation method thereof

The invention relates to a plastic thermosetting resin and a preparation method thereof, in particular to a plastic thermosetting resin of polymethacrylate series and a preparation method thereof.

Polymethacrylate resin is one of the thermoplastic resins that are widely used in daily life, and its advantages include plasticity and dimensional stability. However, polymethacrylate-based resins have some disadvantages, including low chemical resistance, low heat resistance, and low mechanical properties.

In order to solve the above shortcomings, a crosslinking agent is generally added to the polymethacrylate resin to cure it to form a thermosetting resin to improve its chemical resistance, heat resistance and mechanical properties. However, this method will make the polymethacrylate resin The resin loses its original plasticity.

In view of this, how to improve the chemical resistance, heat resistance, and mechanical properties of the polymethacrylate resin while maintaining the plasticity of the polymethacrylate resin itself has become the goal of the relevant industry.

One purpose of the present invention is to provide a method for preparing a plastic thermosetting resin, which utilizes methacrylate-based monomers and glycidyl methacrylate to copolymerize, and then uses a crosslinking agent and a transesterification catalyst to cure the copolymer Cross-linking to form a plastic thermosetting resin with covalently adapted networks (CANs).

Another object of the present invention is to provide a plastic thermosetting resin, which has strong stress and greater strain, as well as good chemical resistance and heat resistance, and can also achieve the original plasticity and repairability at high temperatures .

One embodiment of the present invention is to provide a method for preparing a plastic thermosetting resin, which includes a synthesis step and a crosslinking curing step. Wherein, the aforementioned synthesis step is to synthesize a methacrylate-based monomer and glycidyl methacrylate through a polymerization method to obtain a copolymer. The aforementioned cross-linking curing step is to react the copolymer and a bifunctional cross-linking agent under the catalysis of an ester exchange catalyst to obtain a plastic thermosetting resin.

According to the method for preparing a plastic thermosetting resin according to the foregoing embodiment, the methacrylate-based monomer may be methyl methacrylate, ethyl methacrylate or butyl methacrylate.

According to the preparation method of the plastic thermosetting resin according to the foregoing embodiment, the polymerization method may be free radical polymerization (FRP) or assisted activation and reduction atom transfer radical polymerization (SARA ATRP).

According to the method for preparing a plastic thermosetting resin according to the foregoing embodiment, the copolymer may be a random copolymer, which is obtained by a radical polymerization method or a copolymerization method of assisted activation and reduction atom transfer radical polymerization.

According to the method for preparing a plastic thermosetting resin according to the foregoing embodiment, the copolymer may be a gradient copolymer, which is obtained by the assisted activation and reduction atom transfer radical polymerization method.

According to the preparation method of the plastic thermosetting resin according to the foregoing embodiment, the content of the glycidyl methacrylate in the copolymer is less than 25 mol%.

According to the method for preparing the plastic thermosetting resin of the foregoing embodiment, the bifunctional crosslinking agent may be adipic acid or diamine.

According to the method for preparing a plastic thermosetting resin according to the foregoing embodiment, the synthesis step may further include adding an initiator, wherein the initiator may be azobisisobutyronitrile (AIBN) or ethyl 2-bromoisobutyrate Esters (EBiB).

Another embodiment of the present invention is to provide a plastic thermosetting resin prepared by the aforementioned preparation method.

According to the plastic thermosetting resin of the foregoing embodiment, the stress of the plastic thermosetting resin may be 18 MPa to 70 MPa.

Thus, the present invention uses free radical polymerization or auxiliary activation and reduction atom transfer free radical polymerization to copolymerize methacrylate monomers and glycidyl methacrylate into random copolymers or gradient copolymers, and then copolymerize them. Compound, cross-linking agent and transesterification catalyst are prepared into plastic thermosetting resin with covalent adaptation network (CANs), so that the plastic thermosetting resin of the present invention not only has chemical resistance, heat resistance and high mechanical properties, and its At high temperatures, dynamic covalent exchange reaction (dvnamic covalent change reaction) exchanges the covalent bonds in the network to achieve the plasticity and repairability of the resin.

100‧‧‧Preparation method of plastic thermosetting resin

110, 120‧‧‧ steps

In order to make the above and other objectives, features, advantages and embodiments of the present invention more comprehensible, the description of the accompanying drawings is as follows: Figure 1 shows a plastic thermosetting resin according to one embodiment of the present invention ^{Figure 2 shows the 1} H-NMR spectrum of Synthesis Example 1 to Synthesis Example 5 ^{; Figure 3 shows the 1} H-NMR spectrum of Synthesis Example 7 to Synthesis Example 8; ^{Fig. 4 shows the 1} H-NMR spectra of Synthesis Example 10 to Synthesis Example 11; Fig. 5A shows the relationship between ln(M ₀ /M) and time ^{of ATRP RCP synthesized by MMA and GMA; Fig. 5B} The figure shows the relationship between the molecular weight distribution and conversion rate ^{of ATRP} RCP synthesized by MMA and GMA; Figure 5C shows the relationship between the molecular weight and conversion rate ^{of ATRP RCP synthesized by MMA and GMA; Figure 5D shows the relationship between MMA The distribution graph of the molecular weight of ATRP} RCP synthesized with GMA over time; Fig. 6A shows the relationship between ln(M ₀ ^{/M) and time of ATRP} RCP synthesized with EMA and GMA; Fig. 6B shows the synthesis of EMA and GMA molecular weight ^ATRP RCP of over time profile; 7A of FIG line shows BMA with GMA synthesis of ^ATRP RCP of ln (M ₀ / M) vs. time graph; 7B of FIG line shows BMA with GMA synthesis of ^ATRP RCP ^{Figure 8 shows the 1} H-NMR spectrum of Synthesis Example 12 to Synthesis Example 14 ^{; Figure 9 shows the 1} H-NMR spectrum of Synthesis Example 15 to Synthesis Example 16; ^{Figure 10 shows the 1} H-NMR spectrum of Synthesis Example 17 to Synthesis Example 18; Figure 11A shows the relationship between ln(M ₀ /M) and time ^{of ATRP GCP synthesized by MMA and GMA; Figure 11B} It shows the relationship between the molecular weight distribution and conversion rate ^{of ATRP} GCP synthesized by MMA and GMA; Figure 11C shows the relationship between the molecular weight and conversion rate ^{of ATRP GCP synthesized by MMA and GMA; Figure 11D shows the relationship between MMA and GMA} The distribution graph of the molecular weight ^{of ATRP} GCP synthesized by GMA ^{over time; Figure 12 shows the relationship between PGMA in ATRP} GCP and polymer chain length; Figure 13 shows the ¹ H-NMR of Synthesis Example 19 to Synthesis Example 20 Spectrogram; Figure 14 shows the FTIR diagram of the plastic thermosetting resin before and after curing; Figure 15 shows the stress-strain diagrams of Comparative Example 1, Example 1 to Example 4; Figure 16 Shows the stress-strain diagrams of Example 9 to Example 11; Figure 17 shows the stress-strain diagrams of Example 16 to Example 17; Figure 18 shows the stress-strain diagrams of Example 5 to Example 6; Figure 19 shows the stress and strain diagrams of Example 12 to Example 13; Figure 20 shows the stress and strain diagrams of Example 7 to Example 8; Figure 21 shows the stress and strain diagrams of Example 14 to Example 15. Stress-strain diagram; 22nd Figure is a DSC analysis chart of Comparative Example 1, Example 1 to Example 4; Figure 23 is a DSC analysis chart of Example 9 to Example 11; Figure 24 is a DSC analysis chart of Example 16 to Example 17 is a DSC analysis chart; Figure 25 is a TGA analysis chart of Comparative Example 1, Example 1 to Example 4; Figure 26 is a TGA analysis chart of Example 9 to Example 11; Figure 27 is a TGA analysis chart Shows the TGA analysis diagrams of Examples 16 to 17; Figure 28 shows a schematic diagram of the transesterification reaction of a plastic thermosetting resin; Figure 29A shows a schematic diagram of the plasticity of a plastic thermosetting resin; and Figure 29B It is a drawing of the tensile test after the fracture of the plastic thermosetting resin is repaired.

The various embodiments of the present invention will be discussed in more detail below. However, this embodiment may be an application of various inventive concepts, and may be implemented in various specific ranges. The specific implementation is for illustrative purposes only, and is not limited to the scope of disclosure.

<Preparation method of plastic thermosetting resin>

Please refer to FIG. 1, which is a flow chart of a method 100 for preparing a plastic thermosetting resin according to an embodiment of the present invention. In Figure 1, the method 100 for preparing a plastic thermosetting resin includes step 110 and step 120.

Step 110 is a synthesis step, which is to synthesize a methacrylate-based monomer and glycidyl methacrylate through a polymerization method to obtain a copolymer, wherein the methacrylate-based monomer of the present invention can be It is but not limited to methyl methacrylate (MMA), ethyl methacrylate (EMA) or butyl methacrylate (BMA), in addition, glycidyl methacrylate (glycidyl methacrylate) The content of methacrylate (GMA) in the copolymer is less than 25 mol%, and its purpose is to maintain the high light transmittance of the plastic thermosetting resin.

In detail, the polymerization method can be free radical polymerization (hereinafter referred to as FRP) or assisted activation and reduction atom transfer radical polymerization (hereinafter referred to as SARA ATRP). The difference between FRP and SARA ATRP is that FRP is produced by thermal cracking. Free radicals, while SARA ATRP uses metal catalysis to generate free radicals. FRP is similar to SARA ATRP because there are many types of polymerizable monomers and the reaction conditions are mild. However, FRP cannot control molecular weight and distribution due to its fast reaction rate. On the contrary, SARA ATRP can control the molecular weight and distribution, and can polymerize different types of polymers. The reaction mechanism of FRP and SARA ATRP is well known in the art, and will not be repeated here.

Step 110 may further include adding an initiator. In detail, FRP and SARA ATRP are initiated by an active ingredient. The active ingredient can be obtained by decomposition of the initiator. The initiator commonly used in the reaction can be but not Limited to peroxides, azo compounds, redox initiators or photoinitiators, different initiators have no effect on the distribution of various polymers, but have different reaction rates. The initiator used in the present invention can be azobisisobutyronitrile (AIBN) or 2-bromoisobutyric acid ethyl ester (EBiB), wherein azobisisobutyronitrile has the right Temperature-sensitive characteristics, suitable for FRP, while SARA ATRP must use a halogen atom structure at one end as the initiator, and the transition metal containing the same halogen atom as a catalyst to generate active groups after oxidation of the metal, so it is used The initiator is ethyl 2-bromoisobutyrate, but the initiator used in FRP and SARA ATRP of the present invention is not limited to the above disclosure.

The copolymer of the present invention can be a random copolymer, which can be obtained by copolymerization of FRP or SARA ATRP. Random copolymer means that two monomers are randomly distributed on the main chain, and none of the monomers can be Longer segments are formed on the main chain. In addition, the copolymer of the present invention may also be a gradient copolymer, which is obtained by copolymerization of SARA ATRP. The gradient copolymer refers to a copolymer in which the monomers change in a gradient from one end of the main chain to the other end. Therefore, the copolymer of the present invention can be divided into three types, namely FRP polymerization random copolymer (hereinafter referred to as ^FRP RCP), SARA ATRP polymerization random copolymer (hereinafter referred to as ^ATRP RCP) and SARA ATRP polymerization gradient copolymer (Hereinafter referred to as ^ATRP GCP).

Step 120 is to perform a crosslinking curing step, which is to react the copolymer and a bifunctional crosslinking agent under the catalysis of an ester exchange catalyst to obtain a plastic thermosetting resin, wherein the bifunctional crosslinking of the present invention The agent can be adipic acid or diamine. In detail, step 120 uses the glycidyl methacrylate in the copolymer as the crosslinking point, and then uses a bifunctional crosslinking agent and a transesterification catalyst to cure and crosslink the copolymer to form a network with reversible exchange linkages. The structure, because of the relationship of the interconnection network, can make the material itself have good heat resistance and mechanical properties.

<Plastic thermosetting resin>

The present invention further provides a plastic thermosetting resin prepared by the aforementioned preparation method, which has stronger stress and larger strain than pure polymethacrylate resin, wherein the plastic thermosetting resin of the present invention The stress of the resin can be 18 MPa to 70 MPa. In addition, the plastic thermosetting resin of the present invention also has good chemical resistance and heat resistance, and at high temperatures, the dynamic covalent exchange reaction (Dynamic Covalent Change Reaction) can be used to make the covalent bonds in the cross-linking network proceed. The transesterification reaction achieves the plasticity and repairability of the resin.

<Synthesis example> 1. Random copolymer synthesized by FRP

Synthesis Example 1 to Synthesis Example 11 of the present invention are random copolymers ( ^FRP RCP) synthesized by FRP. The synthesis method is to combine methacrylate monomers, glycidyl methacrylate (GMA), and azo Diisobutyronitrile (AIBN) and dimethylformamide (DMF) were added to a single-necked round-bottom flask in sequence, and then the long needle was put into the solution and replaced with nitrogen for 20 minutes. After the replacement, the reactor was placed at 70°C The oil pan reacted for 24 hours. After the reaction, the product was re-precipitated with methanol, and then the precipitate was collected, and then the residual solvent was removed in a vacuum oven at 40°C. The resulting product was a white solid. Among them, the methacrylate-based monomer of Synthesis Example 1 to Synthesis Example 5 is methyl methacrylate (MMA), and the methacrylate-based monomer of Synthesis Example 6 to Synthesis Example 8 is ethyl methacrylate (EMA) The methacrylate-based monomers of Synthesis Example 9 to Synthesis Example 11 are butyl methacrylate (BMA), and the reaction equations of Synthesis Example 1 to Synthesis Example 11 are shown in Table 1 below.

The feed ratios of the above Synthesis Example 1 to Synthesis Example 11 are shown in Table 2 below.

2. Random copolymer synthesized by SARA ATRP

Synthesis Example 12 to Synthesis Example 18 of the present invention are random copolymers ( ^ATRP RCP) synthesized by SARA ATRP. The synthesis method is to combine methacrylate monomers, glycidyl methacrylate (GMA), 2 -Ethyl bromoisobutyrate (EBiB), ligand dNbpy, Cu ⁰ , CuBr ₂ and anisole as an internal standard are added to Schlenk bottles in sequence, and the freeze-thaw pump cycle method is used for several times until there are no bubbles. After the nitrogen is discharged, back pressure, put it in an oil pan at 80℃ for reaction, and take samples at an appropriate time. Use gas chromatograph to measure the conversion rate of monomers, and the molecular weight is measured by GPC to understand whether the polymerization kinetics It is still in line with active controllable polymerization. After the reaction is completed, the polymer is diluted with tetrahydrofuran, and the copper catalyst is removed with neutral alumina, re-precipitated with methanol, then the precipitate is collected, and the remaining solvent is removed in a vacuum oven at 40°C. The resulting product is a white solid . Among them, the methacrylate-based monomer of Synthesis Example 12 to Synthesis Example 14 is methyl methacrylate (MMA), and the methacrylate-based monomer of Synthesis Example 15 to Synthesis Example 16 is ethyl methacrylate (EMA) The methacrylate-based monomers of Synthesis Example 17 to Synthesis Example 18 are butyl methacrylate (BMA), and the reaction equations of Synthesis Example 12 to Synthesis Example 18 are shown in Table 3 below.

The feed ratios of the above Synthesis Example 12 to Synthesis Example 18 are shown in Table 4 below.

3. Gradient copolymer synthesized by SARA ATRP

Synthesis Example 19 to Synthesis Example 20 of the present invention are gradient copolymers ( ^ATRP GCP) synthesized by SARA ATRP. The synthesis method is to combine 20 mmol of methacrylate monomer and 0.1 mmol of ethyl 2-bromoisobutyrate. Ester (EBiB), 0.3mmol of ligand PMDETA, 0.16mmol of Cu ⁰ , 0.04mmol of CuBr ₂ and anisole as an internal standard were added to a double-necked round bottom flask in sequence, and the freeze-thaw pump cycle method was used for several times. Nitrogen back pressure until no bubbles emerge, and place it above the oil pan at 80°C. Then add 10 mmol of glycidyl methacrylate (GMA) into the Schlenk bottle, freeze and thaw the pump for several cycles, until no bubbles emerge, draw the glycidyl methacrylate with a long needle and place it on the feeder. When the double-necked round-bottomed flask was put into a 80℃ oil pot for reaction, the glycidyl methacrylate was fed at a rate of 0.5mL/hr or 1mL/hr, and samples were taken at appropriate times, and then gas chromatography The conversion rate of monomers is measured by the instrument, and the molecular weight is measured by GPC. It can be understood whether the polymerization kinetics is still in line with the active controllable polymerization. After the reaction is completed, the polymer is diluted with tetrahydrofuran, and the copper catalyst is removed with neutral alumina, re-precipitated with methanol, then the precipitate is collected, and the remaining solvent is removed in a vacuum oven at 40°C. The resulting product is a white solid . Among them, the methacrylate-based monomer of Synthesis Example 19 to Synthesis Example 20 is methyl methacrylate (MMA), and the reaction equation is shown in Table 5 below.

The feed rate and feed ratio of the above Synthesis Example 19 to Synthesis Example 20 are shown in Table 6 below.

<Example/Comparative Example>

Examples 1 to 17 and Comparative Example 1 of the present invention are the plastic thermosetting resins prepared by the above synthesis examples. The preparation method is to combine the above synthesis examples, adipic acid crosslinking agent and Zn(acac ₂ ) Add the transesterification catalyst to the sample bottle and dissolve it with tetrahydrofuran (THF) to prepare a solution with a solid content of 25%. After that, it was evenly coated on Teflon paper and placed at room temperature for 24 hours, and then preheated by hot pressing at 80°C, 100°C and 120°C for 30 minutes, and then heated in a vacuum oven at 150°C and 180°C for 60 minutes. The solidification will be completed within minutes, and then take it out after cooling. Regarding the synthesis examples and synthesis examples used in Examples 1 to 17 and Comparative Example 1, _{the addition amounts of adipic acid and Zn(acac) 2} are listed in Table 7.

<Identification of Random Copolymer>

Please refer to Figures 2, 3 and 4. Figure 2 shows the ¹ H-NMR spectra of Synthesis Example 1 to Synthesis Example 5, and Figure 3 shows the 1 H-NMR spectrum of Synthesis Example 7 to Synthesis Example 8. ¹ H-NMR spectrogram, Figure 4 shows the ¹ H-NMR spectra of ^{Synthesis Example 10 to Synthesis Example 11. The above 1} H-NMR spectra were all _{analyzed in CDCl 3} solution, and a and b were respectively It represents the characteristic peaks of methacrylate-based monomers and glycidyl methacrylate. From the results of Figure 2, Figure 3, and Figure 4, the output ratios of Synthesis Example 1 to Synthesis Example 5, Synthesis Example 7 to Synthesis Example 8, and Synthesis Example 10 to Synthesis Example 11 can be determined, and GPC analysis is used to confirm them Molecular weight and PDI value. The feed ratio, output ratio, molecular weight and PDI value of Synthesis Example 1 to Synthesis Example 5, Synthesis Example 7 to Synthesis Example 8 and Synthesis Example 10 to Synthesis Example 11 are shown in Table 8 below.

It can be seen from the above results that the molecular weights of Synthesis Example 1 to Synthesis Example 5, Synthesis Example 7 to Synthesis Example 8, and Synthesis Example 10 to Synthesis Example 11 of the present invention are about 16,000 to 22,000, and the PDI value is about 1.6 to 3.0. It shows that the present invention can successfully synthesize random copolymers by using FRP.

Please refer to Figure 5A, Figure 5B, Figure 5C, Figure 5D, Figure 6A, Figure 6B, Figure 7A and Figure 7B, where Figure 5A shows the ln ^{of ATRP RCP synthesized by MMA and GMA} (M ₀ /M) vs. time. Figure 5B shows the relationship between the molecular weight distribution and conversion rate ^{of ATRP} RCP synthesized by MMA and GMA. Figure 5C shows the molecular weight ^{of ATRP RCP synthesized by MMA and GMA.} The graph of the relationship with the conversion rate. Graph 5D shows the distribution graph of the molecular weight ^{of ATRP RCP synthesized by MMA and GMA over time.} Figure 6A is a graph showing the relationship between ln(M ₀ ^{/M) of ATRP} RCP synthesized by EMA and GMA and time, and Figure 6B is a graph showing the molecular weight distribution ^{of ATRP RCP synthesized by EMA and GMA over time.} Figure 7A is a graph showing the relationship between ln(M ₀ ^{/M) of ATRP} RCP synthesized by BMA and GMA and time, and Figure 7B is a graph showing the molecular weight distribution ^{of ATRP RCP synthesized by BMA and GMA over time.}

From the results of Fig. 5A, Fig. 6A and Fig. 7A, it can be seen that ln(M ₀ /M) has first-order reaction kinetics with time, where M ₀ is the initial amount of monomer, and M is the amount of monomer at a certain moment. It can be proved that the polymerization reaction can maintain stable growth. It can be seen from Fig. 5B and Fig. 5C that the molecular weight increases linearly with the increase of the conversion rate, and the experimental molecular weight is roughly consistent with the theoretical molecular weight. In addition, during the synthesis process, the PDI is below 1.3. From Figure 5D, Figure 6B, and Figure 7B, it can be seen that under different polymerization times, the molecular weight has a symmetrical unimodal distribution, and the molecular weight distribution is narrow, which proves that SARA ATRP has the characteristics of controlling the molecular weight and its distribution.

Please refer to Figure 8, Figure 9, and Figure 10. Figure 8 shows the ¹ H-NMR spectrum of Synthesis Example 12 to Synthesis Example 14, and Figure 9 shows the 1 H-NMR spectrum of Synthesis Example 15 to Synthesis Example 16. ¹ H-NMR spectrum, Figure 10 shows the ¹ H-NMR spectrum of ^{Synthesis Example 17 to Synthesis Example 18. The above 1} H-NMR spectrum _{is obtained by analysis in CDCl 3} solution, and a and b are respectively It represents the characteristic peaks of methacrylate-based monomers and glycidyl methacrylate. From the results of Figure 8, Figure 9, and Figure 10, the output ratio of Synthesis Example 12 to Synthesis Example 18 can be determined, and the molecular weight and PDI value can be confirmed by GPC analysis. The feedstock of Synthesis Example 12 to Synthesis Example 18 The ratio, output ratio, molecular weight and PDI value are shown in Table 9 below.

From the above results, it can be seen that the molecular weights of Synthesis Example 12 to Synthesis Example 18 of the present invention are about 23,000 to 30,000, and the PDI value is lower than 1.3, indicating that the present invention can successfully synthesize random copolymers by using SARA ATRP.

<Identification of Gradient Copolymer>

Please refer to Figure 11A, Figure 11B, Figure 11C and Figure 11D. Figure 11A shows the relationship between ln(M ₀ /M) and time ^{of ATRP GCP synthesized by MMA and GMA. Figure 11B} It shows the relationship between the molecular weight distribution and conversion rate ^{of ATRP} GCP synthesized by MMA and GMA ^{. Figure 11C shows the relationship between the molecular weight and conversion rate of ATRP} GCP synthesized by MMA and GMA. Figure 11D shows the relationship between MMA and GMA. The molecular weight distribution graph of the synthesized ^{ATRP GCP over time.}

From the results in Figure 11A, it can be seen that ln(M ₀ /M) has first-order reaction kinetics with time, where M ₀ is the initial amount of monomer, and M is the amount of monomer at a certain moment, which proves that the polymerization reaction can be maintained. Steady growth. From Figure 11B and Figure 11C, it can be seen that the molecular weight increases linearly with the increase of the conversion rate, and the experimental molecular weight is roughly consistent with the theoretical molecular weight. In addition, during the synthesis process, the PDI is below 1.3. It can be seen from Figure 11D that under different polymerization times, the molecular weight has a relatively symmetrical unimodal distribution, and the molecular weight distribution is narrow, which proves that SARA ATRP has the characteristics of controlling the molecular weight and its distribution.

Please refer to Figure 12, which shows ^{the relationship between PGMA and polymer chain length in ATRP} GCP. From the results in Figure 12, the solid line is the instantaneous composition of PGMA with the polymer chain, and the dashed line is the PGMA with the instantaneous composition of the polymer chain. The average composition of the polymer chain. The gradient copolymer is that different monomer units are distributed in the polymer in a gradient arrangement along the polymer chain, and the composition will grow linearly with the polymer chain. Therefore, the The growth trend shows that the present invention can successfully synthesize gradient copolymers by using SARA ATR.

Please refer to Figure 13, which shows the ¹ H-NMR spectrum of ^{Synthesis Example 19 to Synthesis Example 20. The above 1} H-NMR spectrum _{is obtained by analyzing in CDCl 3} solution, and a and b represent methacrylic acid respectively Characteristic peaks of ester monomers and glycidyl methacrylate. From the results in Figure 13, the output ratio of Synthesis Example 19 to Synthesis Example 20 can be determined, and its molecular weight and PDI value can be confirmed by GPC analysis, and the monomer conversion rate can be measured by GC. The progress of Synthesis Example 19 to Synthesis Example 20 The material ratio, output ratio, conversion rate, molecular weight and PDI value are shown in Table 10 below.

<Identification of Plastic Thermosetting Resin>

Please refer to Figure 14, which shows the FTIR diagram of the plastic thermosetting resin before and after curing. From the results in Figure 14, it can be seen that the characteristic peak of the epoxy group is located at 908 cm ^-1 . After the curing reaction, the peak of the characteristic peak of the epoxy group gradually disappears, indicating that the plastic thermosetting resin has been completely cured. The plastic thermosetting resin of the present invention can be divided into three types, namely the plastic thermosetting resin prepared by ^{FRP RCP (hereinafter referred to as FRP} RCP-V), and the plastic thermosetting resin prepared by ^{ATRP RCP (hereinafter referred to as ATRP} RCP- V) prepared by the plasticity and ^ATRP GCP thermosetting resin (hereinafter referred to as ^ATRP GCP-V).

<Analysis of Mechanical Properties>

Please refer to Figure 15, Figure 16, and Figure 17. Figure 15 shows the stress and strain diagrams of Comparative Example 1, Example 1 to Example 4, and Figure 16 shows Example 9 to Example 11. Figure 17 shows the stress-strain diagrams of Examples 16 to 17, in which Comparative Example 1, Example 1 to Example 4, Example 9 to Example 11, and Example 16 to Example The measurement results of stress, strain and Young's modulus of 17 are shown in Table 11 below.

Please refer to Figures 18 and 19, where Figure 18 shows the stress-strain diagrams of Examples 5 to 6, and Figure 19 shows the stress-strain diagrams of Examples 12 to 13, where the embodiment The measurement results of stress, strain and Young's modulus of Example 5 to Example 6 and Example 12 to Example 13 are shown in Table 12 below.

Please refer to Figures 20 and 21. Figure 20 shows the stress-strain diagrams of Examples 7 to 8, and Figure 21 shows the stress-strain diagrams of Examples 14 to 15. The measurement results of stress, strain and Young's modulus of Example 7 to Example 8 and Example 14 to Example 15 are shown in Table 13 below.

It can be seen from the above results that after the tensile test, when ^{the PGMA composition in the FRP} RCP-V segment increases, the crosslink density of the resin can be increased, and its stress and Young's modulus increase with the increase of the PGMA composition, indicating that After the copolymerization of MMA/EMA/BMA and GMA to prepare a plastic thermosetting resin, its mechanical properties can be effectively improved. However, comparing ^FRP RCP-V and ^ATRP RCP-V, when the composition ratio of PGMA is similar, although the Young's modulus is similar to each other, ^{the stress of ATRP} RCP-V is lower than that of ^FRP RCP-V. This shows that The difference in molecular weight distribution will affect the mechanical properties of plastic thermosetting resins. In addition, comparing ^ATRP RCP-V and ^ATRP GCP-V, when the composition ratio of PGMA is similar, although the Young's modulus is similar to each other, ^{the stress of ATRP} GCP-V is higher than that of ^ATRP RCP-V. This shows that The gradient copolymer will affect the mechanical properties of the plastic thermosetting resin.

<Analysis of Thermal Properties>

Please refer to Figure 22, Figure 23, and Figure 24. Figure 22 shows the DSC analysis chart of Comparative Example 1, Example 1 to Example 4, and Figure 23 shows Example 9 to Example 11. Figure 24 shows the DSC analysis chart of Example 16 to Example 17, in which Comparative Example 1, Example 1 to Example 4, Example 9 to Example 11, and Example 16 to Example The measurement results of the glass transition temperature (Tg) of 17 are shown in Table 14 below.

It can be seen from the above results that after the measurement by differential scanning measurement (DSC), when the composition of PGMA in the chain segment increases, the increase in crosslinking density reduces the free volume and hinders the movement of the molecular chain. The Tg of the resin will change with the PGMA. The composition increases and rises, indicating that the plastic thermosetting resin prepared by the copolymerization of MMA and GMA can effectively improve its thermal properties. In addition, comparing ^FRP RCP-V, ^ATRP RCP-V and ^ATRP GCP-V, when the composition ratio of PGMA is similar, due to the special composition arrangement of the gradient copolymer, after the formation of the crossover network, the molecular chains are dense. ^{The Tg of ATRP} GCP-V will be higher than ^FRP RCP-V and ^ATRP RCP-V.

<Thermal Stability Analysis>

Please refer to Figure 25, Figure 26 and Figure 27. Figure 25 shows the TGA analysis diagrams of Comparative Example 1, Example 1 to Example 4, and Figure 26 shows Example 9 to Example 11. TGA analysis chart of Example 16 to Example 17, Figure 27 shows the TGA analysis chart of Example 16 to Example 17, in which Comparative Example 1, Example 1 to Example 4, Example 9 to Example 11, and Example 16 to Example The measurement results of the thermal cracking temperature (Td) of 17 and the char yield (Char yield) are shown in Table 15 below.

From the above results, it can be seen that after ^FRP RCP-V and ^ATRP RCP-V are measured by a thermogravimetric analyzer (TGA), it can be observed that in Comparative Example 1 without GMA, the thermal cracking temperature of 5% is 243℃. When the composition of PGMA in PGMA increases, the Td of the resin will increase with the composition of PGMA. When the composition of PGMA is 6mol%, the maximum pyrolysis temperature can reach 320℃. In addition, compare ^FRP RCP-V, ^ATRP RCP-V and ^ATRP GCP- V. In the case of similar composition ratios of PGMA, the pyrolysis temperature is similar to each other, indicating that the plastic thermosetting resin prepared by copolymerization of MMA and GMA can effectively improve its thermal stability.

<plasticity and repairability>

Please refer to Figure 28, Figure 29A and Figure 29B. Figure 28 is a schematic diagram of the transesterification reaction of a plastic thermosetting resin, Figure 29A is a schematic diagram of the plasticity of a plastic thermosetting resin, and the 29B series The drawing shows the tensile test after the fracture of the plastic thermosetting resin is repaired. From Fig. 28, Fig. 29A and Fig. 29B, it can be seen that at 150°C, through thermal triggering The transesterification reaction occurs, the plastic thermosetting resin can be molded into different shapes, and after the fracture of the plastic thermosetting resin is repaired, through the tensile test, it can be found that the recovered sample has a stress loss compared with the new sample. Not big, indicating that the plasticity thermosetting resin prepared by copolymerizing MMA and GMA can exhibit good plasticity and repairability.

In summary, the present invention provides a plastic thermosetting resin and a preparation method thereof. FRP and SARA ATRP are used to synthesize random copolymers or gradient copolymers from methacrylate monomers and glycidyl methacrylate. The random copolymer or gradient copolymer is cross-linked and cured into a plastic thermosetting resin. Through the tensile test, it is found that the plastic thermosetting resin of the present invention has stronger stress and greater strain than pure polymethacrylic resin, and has good heat resistance, and can exhibit the same performance as normal through transesterification at high temperature. Different plasticity and recyclability of thermosetting resin.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone who is familiar with the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection of the present invention The scope shall be subject to the definition of the attached patent application scope.

100‧‧‧Preparation method of plastic thermosetting resin

110, 120‧‧‧ steps

Claims (10)

A method for preparing a plastic thermosetting resin includes: performing a synthesis step of synthesizing a methacrylate-based monomer and glycidyl methacrylate through a polymerization method to obtain a copolymer; and performing a The cross-linking curing step is to react the copolymer with a bifunctional cross-linking agent under the catalysis of an ester exchange catalyst to obtain the plastic thermosetting resin. The method for preparing a plastic thermosetting resin as described in item 1 of the scope of patent application, wherein the methacrylate-based monomer is methyl methacrylate, ethyl methacrylate or butyl methacrylate. The method for preparing a plastic thermosetting resin as described in item 1 of the scope of patent application, wherein the polymerization method is free radical polymerization (FRP) or assisted activation and reduction atom transfer radical polymerization (SARA ATRP). The method for preparing a plastic thermosetting resin as described in item 3 of the scope of patent application, wherein the copolymer is a random copolymer which is copolymerized by the radical polymerization method or the auxiliary activation and reduction atom transfer radical polymerization method And gotta. The method for preparing a plastic thermosetting resin as described in item 3 of the scope of patent application, wherein the copolymer is a gradient copolymer, which is obtained by copolymerization of the auxiliary activation and reduction atom transfer radical polymerization method. The method for preparing the plastic thermosetting resin as described in the first item of the scope of patent application, wherein the content of the glycidyl methacrylate in the copolymer is less than 25 mol%. The method for preparing a plastic thermosetting resin as described in item 1 of the scope of patent application, wherein the bifunctional crosslinking agent is adipic acid or diamine. The method for preparing plastic thermosetting resin as described in item 1 of the scope of patent application, wherein the synthesis step further comprises: adding an initiator, wherein the initiator is azobisisobutyronitrile (AIBN) or 2-bromo Ethyl isobutyrate (EBiB). A plastic thermosetting resin prepared by the method for preparing a plastic thermosetting resin as described in any one of items 1 to 8 of the scope of the patent application. The plastic thermosetting resin described in item 9 of the scope of patent application, wherein the stress of the plastic thermosetting resin is 18 MPa to 70 MPa.

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